CN101481760A - Rolled copper foil and manufacturing method of rolled copper foil - Google Patents
Rolled copper foil and manufacturing method of rolled copper foil Download PDFInfo
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- CN101481760A CN101481760A CNA2009100016070A CN200910001607A CN101481760A CN 101481760 A CN101481760 A CN 101481760A CN A2009100016070 A CNA2009100016070 A CN A2009100016070A CN 200910001607 A CN200910001607 A CN 200910001607A CN 101481760 A CN101481760 A CN 101481760A
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Abstract
A rolled copper foil, according to the present invention, obtained after a final cold rolling step but before recrystallization annealing includes a group of crystal grains which exhibits four-fold symmetry in results obtained by X-ray diffraction (XRD) pole figure measurement with respect to a rolled surface. In the XRD pole figure measurement, at least four peaks of a {220}Cu plane diffraction of a copper crystal due to the group of crystal grains exhibiting the four-fold symmetry, which is obtained during beta axis scanning with an alpha angle set to 45 DEG , appear at intervals of 90 DEG +-5 DEG along the beta angle.
Description
Technical field
The present invention relates to rolled copper foil, relate in particular to the rolled copper foil that is applicable to pliability distribution components such as flexible printed circuit board with good curved characteristic.
Background technology
Flexible printed circuit board (Flexible Printed Circuit is hereinafter referred to as FPC), because it has thin thickness and the good advantage of pliability, thereby very high to the degree of freedom of the mounting means of electronics.Therefore, now, FPC is widely used in the first-class moving part of bending part, digital camera, printer of folder-type portable phone, and the distribution of the moving part of the equipment relevant with CD such as hard disk drive (HDD-Hard Disk Drive), digital versatile disc (DVD-DigitalVersatile Disk) and compact disk (CD-Compact Disk) etc.
As the electrical conductor of FPC, usually use and carried out various surface-treated pure copper foil or copper alloy foil (below, abbreviate " Copper Foil " as).Copper Foil is according to the difference of its manufacture method and be divided into electrolytic copper foil and rolled copper foil roughly.FPC as mentioned above owing to be used as repeatedly the wiring material of active part, thereby, require it to have good curved characteristic (for example, the curved characteristic more than 1,000,000 times).As Copper Foil, often use rolled copper foil.
Generally, the manufacturing of rolled copper foil is carried out as follows: the ingot bar as raw-material reverberatory refining copper (JIS H3100 C1100) and oxygen free copper (JIS H3100 C1020) is being carried out after the hot rolling, carrying out the cold rolling and process annealing thickness up to regulation repeatedly.The desired thickness of the rolled copper foil that FPC uses below 50 μ m, further is thinned to the following tendency of ten number μ m but have recently usually.
The manufacturing process of FPC roughly comprises following operation: " FPC is pasted together and forms the operation of covering copper lamination (CCL-Copper CladedLaminate) with Copper Foil with by the counterdie (body material) that resins such as poly-inferior acyl ammonia constitute "; " utilize etching etc. on this CCL, to form the operation of circuit layout ", " on this circuit, being used to protect the surface treatment procedure of distribution " etc.In the CCL operation, following two kinds of methods are arranged: a kind of be by means of binding agent with Copper Foil and body material lamination after, make adhesive cures fit tightly the method for (3 layers of CCL) by thermal treatment; Another kind is not by means of binding agent, and after directly sticking on surface treated Copper Foil on the body material, makes the method for its integrated (2 layers of CCL) by heating, pressurization.
At this, in the manufacturing process of FPC,, be used to complete the Copper Foil of cold rolling processing (the hard state after the work hardening) from the viewpoint of property easy to manufacture more.This be because, if Copper Foil is in the state of anneal (softening), then carry out severing and during with the lamination of body material at Copper Foil, be easy to produce the distortion (for example, extend, wrinkling, fracture etc.) of Copper Foil, it is bad to occur goods easily.
On the other hand, the curved characteristic of Copper Foil increases significantly than finishing cold rolling machining state by carrying out recrystallization annealing.Therefore, be used for making the body material of above-mentioned CCL operation and Copper Foil fits tightly or incorporate thermal treatment, generally all selecting to carry out simultaneously the manufacture method of the recrystallization annealing of Copper Foil.And heat-treat condition at this moment is 180-300 ℃ 1-60 minutes down (are typically 200 ℃ following 30 minutes), and Copper Foil becomes the modified state of recrystallized structure that is.
In order to improve the curved characteristic of FPC, the curved characteristic that improves as its raw-material rolled copper foil is effective.Be well known that generally cubes texture reaches all the more, the curved characteristic of the Copper Foil after the recrystallization annealing is improved more.And generally said " cubes texture reaches all the more " only is meant in rolling surface, { the occupation rate height of 200}Cu face (for example, more than 85%).
All the time, as curved characteristic good rolled copper foil and manufacture method thereof, report has a following method: the total reduction by improving final cold rolling process (for example, more than 90%), make the method for cubes texture prosperity, with the Copper Foil of the development degree of having stipulated the cubes texture after the recrystallization annealing (for example, the big Copper Foil more than 20 times of intensity of the strength ratio of (200) face of trying to achieve with X-ray diffraction of rolling surface (200) face of trying to achieve with powder x-ray diffraction).Make the prosperity of cubes texture in advance during process annealing before final cold rolling process, the total reduction of final cold rolling process is reached more than 93%, make the flourishing more method of cubes texture behind the recrystallize.Stipulated the Copper Foil (for example, running through crystal grain in the cross-sectional area rate is Copper Foil more than 40%) of the ratio that runs through crystal grain of Copper Foil thickness of slab direction.Controlled the Copper Foil (for example, being controlled to be the Copper Foil of 120-150 ℃ semi-softening temperature) of softening temperature by the interpolation element that adds trace.Stipulated Copper Foil (the every 1mm of twin boundary that for example, surpasses length 5 μ m of twin boundary length
2The combined length of unit surface be the following Copper Foil of 20mm).The Copper Foil of having controlled recrystallized structure by the interpolation element that adds trace (for example, by adding the Sn of 0.01-0.2 quality %, average crystal grain diameter is controlled at below the 5 μ m, maximum crystal grain diameter is controlled at Copper Foil below the 15 μ m) etc. (for example, with reference to patent documentation 1-7).
Patent documentation 1-TOHKEMY 2001-262296 communique,
Patent documentation 2-No. 3009383 communiques of Japan's special permission,
Patent documentation 3-TOHKEMY 2001-323354 communique,
Patent documentation 4-TOHKEMY 2006-117977 communique,
Patent documentation 5-TOHKEMY 2000-212661 communique,
Patent documentation 6-TOHKEMY 2000-256765 communique,
Patent documentation 7-TOHKEMY 2005-68484 communique.
As mentioned above, being reported to of prior art, the total reduction of final cold rolling process is high more, and the cubes texture of rolled copper foil reaches all the more after the recrystallization annealing, and its bending property is improved more.Yet in cold rolling processing, because total reduction is high more, material (Copper Foil) is hard more because of work hardening, thereby, the draught in each road is become restive, the problem that exists the manufacturing efficient of rolled copper foil to reduce.Concrete is, if cold rolling total reduction reaches about 90% or more (particularly more than 93%), then control and the rolling processing itself to the draught in each road all becomes difficult sharp.
On the other hand, in recent years,, the requirement of the high curved characteristic of FPC is compared to pass by further raising along with the progress of the miniaturization of electronics class, highly integrated (the real dressization of high-density) and high performance.Because the curved characteristic of FPC is in fact by the curved characteristic decision of Copper Foil, thereby, in order to satisfy the further curved characteristic of raising Copper Foil of this requirements.On the other hand, also strong request to the cost degradation of electronic component.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of pliability distribution component that is suitable for flexible printed circuit board (FPC) etc., and have the rolled copper foil of good curved characteristic.Have again, in final cold rolling process, do not implementing existing high total reduction even provide a kind of, also can stablize and effectively (that is, with low cost) make the manufacture method of rolled copper foil with high curved characteristic.
The present inventor learns the metallic crystal of rolled copper foil and has carried out finding after the detailed research, has specific correlationship between the state of orientation of the crystal grain after orientation, state of orientation and the recrystallization annealing of the crystal grain of the rolled copper foil behind rolled copper foil behind rough annealing before the final cold rolling process and the final cold rolling process before the recrystallization annealing and the curved characteristic of Copper Foil.In addition, based on having found to think this phenomenon and the different phenomenon of confessed principle so far, and finished the present invention's (detailed content will in aftermentioned).
In order to achieve the above object, rolled copper foil provided by the invention is the rolled copper foil before the recrystallization annealing behind final cold rolling process, it is characterized in that, measuring among the result obtain by the X-ray diffraction pole graph that with the rolling surface is benchmark, have the β angle at least each 90 ± 5
0α angle=45 that exist pole graph to measure
0{ the 220} of the copper crystal that obtains by β scanning
CuThe face diffraction peak is also represented symmetric crystal grain 4 times.
In addition, in order to achieve the above object, rolled copper foil provided by the invention is in the rolled copper foil of the invention described above, it is characterized in that, represents that above-mentioned 4 symmetric diffraction peaks are with respect to the above-mentioned { 220} that is scanned the copper crystal that obtains by β
CuThe minimum strength of face diffraction has the diffracted intensity more than 1.5 times.
In addition, in order to achieve the above object, rolled copper foil provided by the invention is in the rolled copper foil of the invention described above, it is characterized in that, measuring among the result who obtains by the X-ray diffraction pole graph that with the rolling surface is benchmark, in the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by β scanning of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, in α=25-35
0Between have the maximum value P of above-mentioned stdn intensity, in α=40-50
0Between have the maximum value Q of above-mentioned stdn intensity, in α=85-90
0Between above-mentioned stdn intensity increase monotonously; Above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90
0The value R of above-mentioned stdn intensity be " Q≤P≤R ".
In addition, in order to achieve the above object, rolled copper foil provided by the invention is in the rolled copper foil of the invention described above, it is characterized in that, is being measured among the result who obtains by the X-ray diffraction 2 θ/θ to the rolling face, and the diffraction peak intensity of copper crystal is " I{200}
Cu〉=I{220}
Cu".
In order to achieve the above object, rolled copper foil provided by the invention is to have implemented the rolled copper foil after the recrystallization annealing behind final cold rolling process, it is characterized in that, from the ratio [A] of X-ray diffraction 2 θ of rolling surface/θ being measured the cubes texture of calculating, to the crystal grain of this cubes texture outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] and to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.
In order to achieve the above object, the manufacture method of rolled copper foil provided by the invention, the rolling surface that is the rolled copper foil before the recrystallization annealing after with final cold rolling process is being measured among the result obtain by the X-ray diffraction pole graph of benchmark, have the β angle each 90 ± 5
0α angle=45 that exist pole graph to measure
0{ the 220} of the copper crystal that obtains by β scanning
CuThe face diffraction peak is also represented the manufacture method of the rolled copper foil of 4 symmetric crystal grain, it is characterized in that, behind above-mentioned final cold rolling process in the later rolling pass of second passage, comprise and have than one of the rolling pass of next-door neighbour's the big draught more than 1.1 times of last reduction in pass more than the passage.
In addition, in order to achieve the above object, the manufacture method of rolled copper foil provided by the invention is in the manufacture method of the rolled copper foil of the invention described above, it is characterized in that the draught that a final passage in the above-mentioned final cold rolling process or a final preceding passage have an approximately maximum passage in the later rolling pass of second passage.
In addition, in order to achieve the above object, the manufacture method of rolled copper foil provided by the invention is in the manufacture method of the rolled copper foil of the invention described above, it is characterized in that, the total reduction of above-mentioned final cold rolling process is more than 80% below 90%.
In order to achieve the above object, the manufacture method of rolled copper foil provided by the invention, the rolling surface that is the rolled copper foil before the recrystallization annealing after with final cold rolling process is being measured among the result obtain by the X-ray diffraction pole graph of benchmark, have the β angle at least each 90 ± 5
0α angle=45 that exist pole graph to measure
0{ the 220} of the copper crystal that obtains by β scanning
CuThe face diffraction peak is also represented symmetric crystal grain 4 times;
In the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by β scanning of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, in α=25-35
0Between have the maximum value P of above-mentioned stdn intensity, in α=40-50
0Between have the maximum value Q of above-mentioned stdn intensity, in α=85-90
0Between above-mentioned stdn intensity increase monotonously; Above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90
0The value R of above-mentioned stdn intensity be " Q≤P≤R "; It is characterized in that,
The rolling surface of the rolled copper foil after with rough annealing before the above-mentioned final cold rolling process is being measured among the result who obtains by the X-ray diffraction pole graph of benchmark, in the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by β scanning of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, at α=40 ∽ 50
0Between have the maximum value Q of above-mentioned stdn intensity, at α=20 ∽ 40
0Between have the mnm. S of above-mentioned stdn intensity, be that the rolled copper foil of " 2≤Q/S≤3 " is as the annealing blank with the ratio of above-mentioned maximum value Q and above-mentioned mnm. S;
The total reduction of above-mentioned final cold rolling process is more than 80% below 93%.
According to the present invention, the pliability distribution component that is suitable for flexible printed circuit board (FPC) etc. can be provided, and have the rolled copper foil of good curved characteristic.Have again, can provide can stablize and effectively (that is, with low cost) make the manufacture method of rolled copper foil with high curved characteristic.
Description of drawings
Fig. 1 is the synoptic diagram of the oikocryst face of the relevant copper crystal of the present invention of expression.
Fig. 2 is the sketch of relation of incident X-rays, detector, sample, the scan axis of expression X-ray diffraction.
Fig. 3 is in rolled copper foil of the present invention, behind final cold rolling process and under the state before the recrystallization annealing, rolling surface has been carried out the result's of X-ray diffraction 2 θ/θ mensuration a example.
Whether good Fig. 4 be the synoptic diagram of relation of half breadth, the integral breadth of expression crystalline orientation and diffraction peak.
Fig. 5 is the schema of an example of the manufacturing process of expression rolled copper foil of the present invention.
Fig. 6 has carried out orientation mensuration (α=45 in the face to the rolled copper foil of finishing final cold rolling process
0{ 200}
CuThe mensuration of face) result's a example, Fig. 6 (a) is embodiment 1, Fig. 6 (b) is a comparative example 1.
Fig. 7 is an example that the rolled copper foil of finishing final cold rolling process of comparative example 1 has been carried out the result of 2 θ/θ mensuration.
Fig. 8 be to annealing blank rolling surface carried out { 200}
CuThe result's that the XRD pole graph of face is measured a example, Fig. 8 (a) is embodiment 2, and Fig. 8 (b) is embodiment 3, and Fig. 8 (c) is a comparative example 2, and Fig. 8 (d) is a comparative example 3.
Fig. 9 is that the rolling surface to the rolled copper foil in the final cold rolling process process has carried out { 200}
CuThe result's that the XRD pole graph of face is measured a example, Fig. 9 (a) is embodiment 2, and Fig. 9 (b) is embodiment 3, and Fig. 9 (c) is a comparative example 2, and Fig. 9 (d) is a comparative example 3.
Figure 10 has carried out { 200} to the rolled copper foil of finishing final cold rolling process
CuThe result's that the XRD pole graph of face is measured a example, Figure 10 (a) is embodiment 2, and Figure 10 (b) is embodiment 3, and Figure 10 (c) is a comparative example 2, and Figure 10 (d) is a comparative example 3.
Figure 11 is an example that the rolled copper foil of finishing final cold rolling process has been carried out the result of 2 θ/θ mensuration, and Figure 11 (a) is embodiment 2, and Figure 11 (b) is embodiment 3, and Figure 11 (c) is a comparative example 2.
Figure 12 is a schematic synoptic diagram of having represented curved characteristic evaluation (slip pliability test).
Among the figure:
The 1-Copper Foil, 2-tests retaining plate, the 2a-screw, 3-vibrates transfer part, 4-exciting driving body, R-curvature.
Embodiment
Fig. 1 is the synoptic diagram of the oikocryst face of the relevant copper crystal of the present invention of expression.Because the crystalline structure of copper is a cubes, thereby, { 200}
CuFace and { 220}
CuThe angle that face forms is 45
0And, { } expression face (with reference to Fig. 1) of equal value.
Fig. 2 is the sketch of relation of incident X-rays, detector, sample, the scan axis of expression X-ray diffraction (below, the occasion that also useful XRD represents).Below, with Fig. 2 the relevant evaluation method of XRD to the grain orientation state of rolled copper foil of utilizing is described.In addition, three scan axises of Fig. 2 generally are called the sample axle with the θ axle, the α axle is called door-hinge, the β axle is called the rotating shaft of face inward turning.In addition, X-ray diffraction of the present invention all utilizes Cu K α line.
With respect to incident X-rays, will scan sample and detector at the θ axle, be the sweep angle of sample with the θ angle, be that measuring method that the sweep angle of detector scans is called 2 θ/θ and measures with 2 θ angles.Utilization can be estimated in the sample face (being rolling surface in the present invention) as multicrystal rolled copper foil by the intensity that 2 θ/θ measures the diffraction peak that obtains, and which crystal face has advantage.
Be conceived to some diffraction surfaces { hk1}
Cu, with respect to { the hk1} that has in mind
Cu2 θ values, (sweep angle 2 θ of fixed detector) are called swing curve with the measuring method that only sample is carried out the scanning of θ axle and measure.{ the hk1} that utilization is obtained by this mensuration
CuThe half breadth of face peak value or integral breadth can be estimated { hk1}
CuThe orientation degree of the rolling surface vertical direction of face.At this moment we can say that the value of half breadth or integral breadth is more little, with the crystalline orientation of rolling surface vertical direction good more (below, " with the crystalline orientation of rolling surface vertical direction " is called the outer orientation of face).In addition, half breadth is defined as the spike width of a half intensity of the maximum strength of diffraction peak, and integral breadth is defined as the result who removes the integrated intensity of diffraction peak with the maximum strength of this diffraction peak.One of evaluation method of having utilized the feature that pole graph measures has in the face orientation measure.This measuring method is, will with { the hk1} that has in mind
CuThe crystal face of face geometry correspondence { h ' k ' 1 ' }
CuAnd this { hk1}
CuThe angle that face forms is made as α ' time, carries out α axle scanning (sample is tilted) in the mode of " α=90-α ' ", and with respect to { h ' k ' 1 ' }
Cu2 θ values of face (sweep angle 2 θ of fixed detector) are carried out β axle scanning (at face internal rotation (rotation) up to 0-360 to sample
0).{ h ' k ' 1 ' } that use is obtained by this mensuration
CuThe half breadth of face peak value or integral breadth can be estimated and { h ' k ' 1 ' }
Cu{ the hk1} of face geometry correspondence
CuTwo axial orientation degree in the rolling surface of face.At this moment, with above-mentioned same, we can say that the half breadth of this diffraction peak or the value of integral breadth are more little, the crystalline orientation of direction is good more in the rolling surface.(below, " crystalline orientation of direction in the rolling surface " is called " orientation in the face ").In addition, in XRD pole graph of the present invention is measured, will be defined as α=90 with the vertical direction of sample face
0, and as measuring benchmark.In addition, though pole graph is measured reflection method (α=15 ∽ 90 is arranged
0) and transmission method (α=0 ∽ 15
0), but pole graph of the present invention mensuration is only considered reflection method (α=15 ∽ 90
0) mensuration.
(first embodiment of the present invention)
(orientation is measured in the face)
The rolled copper foil of present embodiment is the rolled copper foil before the recrystallization annealing behind final cold rolling process, it is characterized in that, by being that the X-ray diffraction pole graph of benchmark is measured the result who obtains with the rolling surface, exist in the β angle at least each 90 ± 5
0α angle=45 that exist pole graph to measure
0{ the 220} of the copper crystal that obtains by β axle scanning
CuThe face diffraction peak also shows symmetry 4 times.For example, the rolling direction at the Copper Foil that pole graph is measured is made as β=0
0The time, the center of 4 subsymmetric diffraction peaks is respectively β ≌ 0
0, 90
0, 180
0, 270
0, 360
0
Among the result that orientation is measured in above-mentioned, and 220}Cu face diffraction peak do not show each 90 ± 5
04 symmetry the time, even then implemented the rolled copper foil that recrystallization annealing can not obtain having high curved characteristic.Therefore, as above stipulate.In addition, so-called α angle=45 of measuring at pole graph
0The time copper crystal that obtains by β axle scanning { 220}
CuThe face diffraction peak each 90 ± 5
0Show that 4 symmetry are meant and { 220}
CuFace crystallization geometry ground constitutes 45
0{ the 200} of angle
CuFace is to be orientated in the face at the rolling surface of Copper Foil.In addition, these 4 symmetric diffraction peaks preferably separately diffraction peak intensity with respect to by β axle scanning (at 0 ∽ 360
0The face internal rotation) { the 220} of the copper crystal that obtains
CuThe minimum strength that face spreads out has more than 1.5 times.
(second embodiment of the present invention)
(stdn intensity)
The rolled copper foil of present embodiment is the rolled copper foil before the recrystallization annealing behind final cold rolling process, it is characterized in that, by being that the X-ray diffraction pole graph of benchmark is measured the result obtain with above-mentioned rolling surface, in the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by the scanning of β axle of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, at α=25 ∽ 35
0Between have the maximum value P of above-mentioned stdn intensity, at α=40 ∽ 50
0Between have the maximum value Q of above-mentioned stdn intensity, at α=85 ∽ 90
0Between above-mentioned stdn intensity increase above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90 monotonously
0The value R of above-mentioned stdn intensity be " Q≤P≤R ".In the result that the pole graph of above-mentioned XRD is measured, as { 220}
CuThe stdn intensity of face diffraction peak does not show α=25 ∽ 35
0Maximum value P and α=40 ∽ 50
0Maximum value Q and α=85 ∽ 90
0Increase monotonously, in above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90
0The value R of stdn intensity when not showing concerning of " Q≤P≤R ", even carried out recrystallization annealing, can not obtain having the rolled copper foil of high curved characteristic.Therefore, as above stipulate.
In addition, stdn intensity Rc is in the XRD pole graph is measured, { the hk1} of the regulation that will be obtained by the β axle scanning (face inward turning rotating shaft scanning) of each α angle
CuThe counting that diffraction peak averages, and can calculate with following formula.And the logical conventional computer of standardized calculating is carried out.
Rc＝Ic/Istd
Wherein, Ic: corrected strength (the background correction absorbs and revises)
Istd: be used for standardized intensity by what calculating was tried to achieve.
Document name: " RAD system software texture analysis program process specifications (specification sheets numbering: MJ201RE) ", Rigaku Denki Co., Ltd, p.22 ∽ 23.
Document name: " the anodal point operation specification sheets of CN9258E101 RINT2000 serial application software (specification sheets numbering: MJ10102A01) ", Rigaku Denki Co., Ltd, p.8 ∽ 10.
In addition, comparatively speaking the reason that the stdn of XRD peak strength is used is, the influence (not installing dependency in fact) of tube voltage when avoiding XRD determining and tube current etc.
(the 3rd embodiment of the present invention)
(2 θ/θ measures)
The rolled copper foil of present embodiment is characterized in that, under the state behind final cold rolling process before the recrystallization annealing, measures the result who obtains by the X-ray diffraction 2 θ/θ to the rolling face, and the intensity I of the diffraction peak of copper crystal is " I{200}
Cu〉=I{220}
Cu".
As mentioned above, rolled copper foil of the present invention behind final cold rolling process under the state before the recrystallization annealing, { 200}
CuFace is orientated in the rolling surface of Copper Foil.This means, on rolling surface, have considerable { 200} as multicrystal Copper Foil
CuThe crystal grain of planar orientation.Fig. 3 is in rolled copper foil of the present invention, behind final cold rolling process and under the state before the recrystallization annealing, rolling surface has been carried out the result's of X-ray diffraction 2 θ/θ mensuration a example.
As can be seen from Figure 3, { the 200} of rolling surface
CuThe diffracted intensity of face is stronger, demonstrates { 200}
CuThe crystal grain of planar orientation exists in a large number.On the rolling surface of Copper Foil, if { 200}
CuFace does not have stronger orientation, even then implement recrystallization annealing, can not obtain having the rolled copper foil of high curved characteristic.Therefore, as above stipulate.
(the 4th embodiment of the present invention)
(comprehensively being orientated ratio)
The rolled copper foil of present embodiment is the rolled copper foil before the recrystallization annealing behind final cold rolling process, it is characterized in that, from the X-ray diffraction 2 θ/θ of rolling surface being measured the ratio [A] of the cubes texture of calculating, with outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] with regard to the crystal grain of this cubes texture, and with regard to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.In the present invention, [A] * [B] * [C] is defined as comprehensive orientation ratio.If comprehensive orientation ratio then can not obtain high curved characteristic less than 0.5 ([A] * [B] * [C]＜0.5).To comprehensively be orientated ratio is set in more than 0.5.More preferably more than 0.55, further preferred more than 0.6.
Secondly, the face of the ratio [A] of cubes texture, cubes texture is orientated outward orientation ratio [C] describes in the face of ratio [B], cubes texture.
The ratio of cubes texture [A] is defined as, and the rolling surface of having implemented the rolled copper foil of recrystallization annealing behind final cold rolling process is carried out X-ray diffraction 2 θ/θ measure, and utilize following formula to calculate to present { the 200} of cubes texture
CuThe diffraction peak of face is to the ratio of whole diffraction peaks.
The ratio of cubes texture [A]=I{200}
Cu/ (I{111}
Cu+ I{200}
Cu+ I{220}
Cu+ I{311}
Cu)
Wherein: I{111}
Cu: { 111}
CuThe diffraction peak intensity of face
I{200}
Cu: { 200}
CuThe diffraction peak intensity of face
I{220}
Cu: { 220}
CuThe diffraction peak intensity of face
I{311}
Cu: { 311}
CuThe diffraction peak intensity of face.
The face of cubes texture is orientated ratio [B] outward and is defined as, to { the 200} of the rolling surface of the rolled copper foil of having implemented recrystallization annealing behind final cold rolling process
CuFace carries out the X-ray diffraction swing curve to be measured, and utilizes following formula to calculate this { 200}
CuThe half breadth of face diffraction peak and the ratio of integral breadth.
The face of cubes texture is orientated ratio [B]=Δ θ outward
FWHM/ Δ θ
IW
Wherein: Δ e
FWHM: { 200}
CuThe spike width of one half intensity of the maximum strength of face diffraction peak,
Δ θ
IW: with { 200}
CuThe maximum strength of face diffraction peak is removed the value of the integrated intensity of this diffraction peak.
Orientation ratio [C] is defined as in the face of cubes texture, is that benchmark carries out α angle=45 with the rolling surface to the rolled copper foil of having implemented recrystallization annealing behind final cold rolling process
0{ 220}
CuThe mensuration X-ray diffraction pole graph of face is measured, and utilizes following formula to calculate the 4 subsymmetric { 220} that obtained by the scanning of β axle
CuIn the diffraction peak of face, the half breadth of any one diffraction peak and the ratio of integral breadth.
Orientation ratio [C]=Δ β in the face of cubes texture
FWHM/ Δ β
IW
Wherein: Δ β
FWHM: { 220}
CuThe spike width of one half intensity of the maximum strength of face diffraction peak,
Δ β
IW: with { 220}
CuThe maximum strength of face diffraction peak is removed the value of the integrated intensity of this diffraction peak.
At this, be orientated in the ratio [C] meaning of the half breadth of employing diffraction peak and the ratio of integral breadth in ratio [B] and the face to outside face, being orientated.Whether good Fig. 4 be the synoptic diagram of relation of half breadth, the integral breadth of expression crystalline orientation and diffraction peak.If in the low rolled copper foil of crystalline orientation, carry out orientation mensuration in swing curve mensuration and the face, shown in Fig. 4 (a), though then obtain near the diffraction peak shape of the steeper portion in peak value center big (broad bottom the curve) easily.On the other hand, if the high rolled copper foil of crystalline orientation is carried out orientation mensuration in swing curve mensuration and the face, shown in Fig. 4 (b), then can obtain diffraction peak and concentrate near the shape in peak value center.
When to these diffraction peak evaluations separately half breadth and during integral breadth, be judged as: at the low occasion of crystalline orientation (Fig. 4 (a)), it is bigger poor to produce in half breadth and the integral breadth; At the high occasion of crystalline orientation (Fig. 4 (b)), the difference of half breadth and integral breadth diminishes.And such difference can think to come from the size (portion in the diffraction peak shape shared size) of the portion of diffraction peak shape.So, by the half breadth of employing diffraction peak and the ratio of integral breadth, compare with comparing half breadth and integral breadth respectively, can more clearly judge the quality of the crystalline orientation of rolled copper foil.
[manufacture method of rolled copper foil]
Below, with reference to the manufacture method of figure explanation rolled copper foil of the present invention.Fig. 5 is the schema of an example of the manufacturing process of expression rolled copper foil of the present invention.
At first, (operation a) to prepare ingot metal (ingot bar) as raw-material reverberatory refining copper (JIS H3100 C1100) and oxygen free copper (JISH3100 C1020) etc.Secondly, carried out enforcement hot rolled hot-rolled process (operation b).Behind hot-rolled process,, make the copper bar that is called as " blank " by suitably implementing cold rolling cold rolling process (operation c) and mitigation process annealing operation (operation d) repeatedly because of the cold rolling work hardening that causes.Then, carry out rough annealing operation (operation d ').In the rough annealing operation, preferably eliminate processing strain (for example, roughly Full Annealing) before this fully.
Thereafter, annealed " blank " (being called the annealing blank) is implemented final cold rolling process (operation e also has the situation that is called " finish rolling operation "), the Copper Foil of making specific thickness is rolling.Rolled copper foil behind the final cold rolling process can carry out (operation f) such as surface treatments as required, supplies with FPC manufacturing process (operation g).As mentioned above, recrystallization annealing (operation g ') often in operation g (for example, CCL operation) carry out.In the present invention, " final cold rolling process " is meant operation e, and " recrystallization annealing " operation g ' is meant the operation of carrying out in operation g.
Here, the feature of one of manufacture method of rolled copper foil of the present invention is, in the later rolling pass of second passage of above-mentioned final cold rolling process, the rolling pass of the big draught more than 1.1 times of draught that has than next-door neighbour's a last rolling pass comprises more than 1 passage.Thus, the terminal stage in this cold rolling processing has strengthened { 220}
CuThe formation of the rolling texture of planar orientation, and then can in this rolling texture, promptly form the kind crystalline substance of cubes tissue.And, can think that the kind crystalline substance of this cubes tissue helps through the height of the cubes texture of recrystallization annealing orientation grow up (details will in aftermentioned).
More preferably, " rolling pass of the big draught more than 1.15 times of draught that has than next-door neighbour's a last rolling pass comprises more than 1 passage.", particularly preferably be that " rolling pass of the big draught more than 1.2 times of draught that has than next-door neighbour's a last rolling pass comprises more than 1 passage.”。With regard to " having the rolling pass than 1.1 times of little draught " of breaking away from afore mentioned rules, the kind crystalline substance that forms the cubes tissue in rolling texture is difficult.
In addition, a passage before final passage in the preferably final cold rolling process or next-door neighbour are final has the draught about a maximum passage in the later rolling pass of the 2nd passage.Thus, the kind crystalline substance that can be suppressed at the cubes tissue that forms in the rolling texture be accompanied by rolling process carrying out and to other orientation rotation (details will in aftermentioned).In addition, be controlled at more than 80% below 90% by total reduction final cold rolling process, except total road number of times that can reduce rolling process, the difficulty of the controlled rolling processing that can also avoid causing because of over-drastic work hardening, and can promote the reduction of manufacturing cost.
In addition, replacing other manufacture method of the rolled copper foil of the present invention of above-mentioned manufacture method is to adjust the manufacture method of annealing blank in the following manner by controlling rough annealing operation (operation d ') at least.In final afterwards cold rolling process (operation e) rolled copper foil (annealing blank) before of rough annealing (operation d '), it is characterized in that, utilization is that the X-ray diffraction pole graph of benchmark is measured among the result who obtains with the rolling surface, in the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by the scanning of β axle of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, at α=40 ∽ 50
0Between have the maximum value Q of stdn intensity, at α=20 ∽ 40
0Between have the mnm. S of stdn intensity, be that the rolled copper foil of " 2≤Q/S≤3 " is as the annealing blank to final cold rolling process with the ratio of above-mentioned maximum value Q and above-mentioned mnm. S.And then it is the final cold rolling process (operation e) below 93% more than 80% that such annealing blank is implemented total reduction.In addition, as the rough annealing condition, preference is as 600
0More than 700
0Below 1-30 minutes condition of (the real attitude temperature of Copper Foil) insulation.More preferably temperature is 650
0More than 700
0Below.
Like this, be that the X-ray diffraction pole graph of benchmark is measured among the result who obtains with the rolling surface in the utilization of final cold rolling process (operation e) recrystallization annealing afterwards (operation g ') rolled copper foil before, exist in the β angle at least each 90 ± 5
0α angle=45 that exist pole graph to measure
0{ the 220} of the copper crystal that obtains by β scanning
CuThe face diffraction peak also shows symmetric crystal grain 4 times; In addition, be transverse axis in the α angle of measuring with pole graph, to scan { the 220} of the copper crystal that obtains by β
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, at α=25 ∽ 35
0Between have the maximum value P of stdn intensity, at α=40 ∽ 50
0Between have the maximum value Q of stdn intensity, at α=85 ∽ 90
0Between stdn intensity increase monotonously, obtain maximum value P and maximum value Q and α=90
0The value R of stdn intensity be the rolled copper foil of the present invention of " Q≤P≤R ".
As mentioned above, { the 220} of copper crystal
CuFace and { 200}
CuFace exists 45 geometrically
0(angle of two crystal plane formation is (45
0) relation.Therefore, can think, at α=40 ∽ 50
0Between exist the maximum value Q of stdn intensity with on the rolling surface of rolled copper foil { 200}
CuThe degree of orientation is relevant in the crystal grain face of face.In other words, the invention is characterized in, in final afterwards cold rolling process (operation e) blank before of rough annealing (operation d '), { 200} that on rolling surface, exists
CuThe crystal grain of orientation is the degree of " Q≤P≤R " through final cold rolling process (operation e) existence pass in planar orientation and the face.
In addition, be controlled at more than 80% by total reduction and compare with the rolled copper foil of existing high draught below 93% final cold rolling process, except total road number of times that can reduce rolling process, the difficulty of the controlled rolling processing that can also avoid causing because of over-drastic work hardening, and can promote the load of minimizing producing apparatus and the reduction of manufacturing cost.
(investigation of the mechanism of high curved characteristic)
Below, the mechanism of the high curved characteristic of the rolled copper foil of embodiments of the present invention is described.When to the Metallic Solids stress application, be easy to generate dislocation moving in the crystal along the crystalline slip plane.Yet the grain boundary generally becomes the obstacle to dislocation moving.In as multicrystal rolled copper foil, when dislocation is transported to when accumulating in grain boundary etc. because of bending, then be easy to generate crackle assembling part, can think to cause so-called metal fatigue.In other words, as long as can in metal polycrystal, suppress the gathering of dislocation, just can expect to improve curved characteristic.
The rolled copper foil of embodiments of the present invention demonstrates and can just can control cubes texture after the recrystallization annealing by the grain orientation state behind control annealing blank and/or the final cold rolling process.Can think, as long as can obtain constructing { the 111} of distinctive slip plane by recrystallize as the face-centered cubic of copper crystal
CuThe cubes texture that the orientation of face (that is, alignment slip direction) is crossed over the grain boundary and is well controlled just can improve the probability that when bending is transported to dislocation causes cross slip thus, and its result just can obtain high curved characteristic.That is, main points are how to form crystal grain and are the cubes texture of 3 D tropism (always being orientated the ratio height) each other.
On the other hand, it is contemplated that " the stress under compression composition " and " tensile stress composition " that is decomposed into object at the rolling stress that man-hour object is applied that adds.In addition, in the cold rolling processing to Copper Foil, the copper crystal in the Copper Foil forms rolling texture owing to the rolling stress that adds man-hour causes rotation phenomenon along with the progress of processing.At this moment, the crystalline gyrobearing that is caused by stress direction (orientation that is orientated on rolling surface) generally is that the occasion of stress under compression is { 220}
CuFace, the occasion of tensile stress are { 311}
CuFace or { 211}
CuFace.Can think, follow the processing strained of these rotation phenomenons to accumulate the motivating force that forms cubes texture when becoming recrystallize.
In existing rolled copper foil, from the point of view, purpose is by setting the total reduction of final cold rolling process higher (for example, more than 93%) and improve stress under compression, thereby improves { 220}
CuPlanar orientation (rolling texture) and the accumulation of processing strained.In addition, as mentioned above,, only be conceived to improve { 200} as cubes texture
CuThe occupation rate of face in rolling surface (perpendicular to the rolling surface direction one-dimension oriented), and will not consider especially the state of orientation in rolling surface (that is crystal grain 3 D tropism each other).But, because along with the material (Copper Foil) that carries out of rolling processing is got over hardening because of work hardening, thereby can expect, general, along with the draught of each passage of carrying out of rolling processing diminishes.
Yet it is relevant with following phenomenon that such mill condition can be thought, that is: because in a single day the passage (rolling pass that the draught of each passage is big) of high draught forms { 220}
CuThe part of the crystal grain of planar orientation is owing to the passage of thereafter low draught begins to { 311}
CuPlanar orientation and { 211}
CuThe planar orientation rotation.This is because can think that for the big rolling pass of the draught of each passage, its " stress under compression composition " preponderates; And for the little rolling pass of the draught of each passage, its " tensile stress composition " preponderates.
To this, one of manufacture method of rolled copper foil of the present invention is in the later rolling pass of second passage of final cold rolling process, has adopted the rolling pass that has than the big draught more than 1.1 times of draught of next-door neighbour's a last rolling pass to comprise mill condition such more than 1 passage.Concrete for example can enumerate, and carries out at the latter half of mill condition that each passage in the later rolling pass of second passage has the formation of passage of maximum draught and the draught of each passage increases such formation later on gradually in second passage.Rolling working method like this becomes and the opposite formation of existing method mill condition.In addition, after second passage of final cold rolling process the latter half of mill condition (particularly), by the high rolling pass of draught of carrying out each passage, thereby distinguish in rolling processing to produce partial recrystallize phenomenon etc. midway, in rolling texture, form kind the crystalline substance ({ 220} of cubes tissue
CuThe crystal grain of planar orientation).And, can think that the kind crystalline substance of this cubes tissue helps the high orientation of the cubes texture of recrystallization annealing and grows up.
On the other hand, other manufacture method of rolled copper foil of the present invention has following method, that is: control is to the annealing blank of final cold rolling process (operation e) supply, at the rolling texture ({ 220} of final cold rolling process (operation e)
CuPlanar orientation) in the forming process, makes remaining cubes the tissue ({ 220} that an amount of (degree that the relation of " Q≤P≤R " is set up) arranged of this rolling texture
CuPlanar orientation) crystal grain.And, can think to have and disperse and remain in the crystal grain of having accumulated the cubes tissue in the processing strained rolling texture to help high orientation growth (particularly 3 D tropism) by the kind trichite effect of waving that the cubes texture as recrystallization annealing forms.
Have again, this manufacture method of rolled copper foil, can think, the total reduction of its final cold rolling process is more than 80% below 93%, in the crystal grain (not producing the crystal grain of the rotation phenomenon of crystal plane) of remaining above-mentioned cubes tissue, to rolled copper foil (for example, the total reduction 93% or more) much less of the processing strained of Copper Foil accumulation than prior art.The motivating force that this atom during with recrystallization annealing rearranges is little relevant, can suppress grow up (thickization of crystal grain) of recrystal grain.Suppress excessively growing up to be related to and to solve " the dish shape depressed phenomenon " that in FPC manufacturing process, becomes problem recently of recrystal grain.When so-called " dish shape depressed phenomenon " is meant in FPC manufacturing process Copper Foil carried out half corrosion, present the phenomenon that the big crystal grain of particle diameter preferentially is corroded, copper foil surface becomes the arc crater shape owing to exist to be inclined to crystal grain unit's corrosive.
[other embodiment of the present invention]
In operation a, to fusing and castmethod without limits, in addition, to the size of material also without limits.Also having no particular limits in operation b, operation c and operation d, can be usual method and condition.In addition, the thickness of the rolled copper foil that FPC uses generally below 50 μ m, the thickness of rolled copper foil of the present invention as long as below 50 μ m all can, be not particularly limited, but below the preferred especially 20 μ m.
[manufacturing of flexible printed circuit board]
Use the rolled copper foil of above-mentioned embodiment, utilize the manufacture method that adopts usually, can obtain flexible printed circuit board.In addition, both can adopt the common thermal treatment of in the CCL operation, carrying out, also can adopt other operation the recrystallization annealing of rolled copper foil.
[effect of embodiment]
Adopt the embodiment of the invention described above, can obtain following effect.
(1) can obtain having the rolled copper foil of the curved characteristic better than prior art.
(2) can stablize and the efficient rolled copper foil made from curved characteristic better than prior art (that is low cost).
(3) can obtain having the pliability wiring of the flexible printed circuit board (FPC) etc. of the curved characteristic better than prior art.
(4) be not only limited to flexible printed circuit board (FPC), can be applied to require other conductive component (for example, need be the negative material etc. of the lithium ion battery used of vibratory automobile) of high curved characteristic (flex life) yet.
Below, illustrate in greater detail the present invention according to embodiment, but the present invention is not subjected to the restriction of these embodiment.
[embodiment]
[embodiment 1-3 and comparative example 1-3]
(production order)
Beginning, as starting material reverberatory refining copper (oxygen level is 150ppm), having made thickness is that 200mm, width are the ingot bar of 650mm., according to the flow process of Fig. 5 record carry out hot rolling up to the thickness of 10mm after, suitably answer and carry out cold rolling repeatedly and process annealing (comprising rough annealing), make annealing blank with 0.2mm and 0.1mm thickness thereafter.As the annealing blank, carried out following processing respectively: be incubated about 1 minute thermal treatment (embodiment 1 and comparative example 1) in about 700 ℃ temperature, be incubated about 2 minutes thermal treatment (embodiment 2) in about 650 ℃ temperature, be incubated about 1 minute thermal treatment (embodiment 3) in about 690 ℃ temperature, be incubated about 2 minutes thermal treatment (comparative example 2) in about 550 ℃ temperature, be incubated about 1 minute thermal treatment (embodiment 3) in about 800 ℃ temperature.In addition, the annealing temperature of blank is not the design temperature of annealing furnace, but the actual temperature of Copper Foil.
Subsequently, by above-mentioned annealing blank is carried out final cold rolling process under the condition shown in table 1 or the table 2, make the rolled copper foil that thickness is 16 μ m (embodiment 1-3 and comparative example 1-3).
(continued on next page)
The condition of the final cold rolling process of table 1
The condition of the final cold rolling process of table 2
(XRD to rolled copper foil estimates)
XRD to rolled copper foil (behind the rough annealing, in the final cold rolling process process, behind the final cold rolling process, after the recrystallization annealing) estimates as follows.In addition, in various XRD determining (2 θ/θ measures, and swing curve is measured, and pole graph is measured, and orientation is measured in the face), X-ray diffraction device (the リ ガ of Co., Ltd. Network system, model: RAD-B) have been used.Anticathode (target) uses copper, and tube voltage and tube current are respectively 49kV, 30mA.And supplying the size of the sample of XRD determining is about 15 * 15mm
2
The condition that XRD2 θ/θ measures uses general wide-angle angle mirror in 2 θ=40-100
0Scope in measure.The slit condition that 2 θ/θ measures is that divergent slit is 1
0, being subjected to optical slits is 0.15mm, scatter slit is 1
0In addition, XRD swing curve mensuration is fixed on detector by XRD2 θ/θ and measures { the 200} that obtains
Cu2 θ values of face diffraction peak to sample at θ=15 ∽ 35
0Carry out sweep measuring in the scope.In addition, the slit condition of swing curve mensuration is measured identical with 2 θ/θ.
The condition that the XRD pole graph is measured and the interior orientation of face is measured uses general Shu Erci reflection method at α=15 ∽ 90
0(direction perpendicular to rolling surface is 90
0) the β angle is carried out 0-360 on one side in the scope
0Scanning (rotation), on one side mensuration { 220}
CuThe diffracted intensity of face is (with 2 θ ≌ 74
0, 2 θ values have been used the result that each sample preparation is measured).This slit condition of knowing is that divergent slit is 1
0, scatter slit=7mm, being subjected to optical slits is 7mm and Shu Erci slit (slit height is 1mm).In addition, orientation is measured and is fixed on α=45 in the face
0Carry out.
(embodiment 1 and comparative example 1)
(finishing the rolled copper foil of final cold rolling process)
Each rolled copper foil (thickness is 16 μ m) to the state of finishing rolling processing of the embodiment 1 that makes as mentioned above and comparative example 1 (behind the final cold rolling process before the recrystallization annealing) has carried out XRD determining.Fig. 6 has carried out orientation mensuration (α=45 in the face to the rolled copper foil of finishing final cold rolling process
0{ 220}
CuThe mensuration of face) result's a example.Fig. 6 (a) is embodiment 1, and Fig. 6 (b) is a comparative example 1.
As indicated in Fig. 6, can think, the rolled copper foil of embodiment 1 each 90 ± 5
0There are 4 symmetric diffraction peaks (representing) with black arrow.In addition, this diffraction peak is with respect to { the 220} that is obtained by β scanning
CuThe minimum strength of face diffraction has the diffracted intensity more than 1.5 times.This means { 220}C in the rolling surface of Copper Foil
uMask has orientation in the good face.With respect to this, with regard to the rolled copper foil of comparative example 1, though can be at β ≌ 0
0(360
0), 180
0See weak diffraction peak, but at β ≌ 90
0, 270
0But almost can not see diffraction peak.
Fig. 7 is an example that the rolled copper foil of finishing final cold rolling process of comparative example 1 has been carried out 2 θ/result that θ mensuration obtains.In addition, Fig. 3 is an example of 2 θ/θ measurement result of embodiment 1.As mentioned above, the rolled copper foil of embodiment 1 shown in Figure 3 is presented at and has a large amount of { 200} on the rolling surface
CuThe crystal grain of planar orientation.At { 200} with Fig. 3
CuDiffraction peak intensity I { the 200} of face
CuBe made as 100 occasion, { 220}
CuDiffraction peak intensity I { the 220} of face
CuBe 48.In addition, as { the 200} that considers the copper crystal powder
CuFace and { 220}
CuWhen the X-ray diffraction intensity ratio of face is about 2:1, can think that the rolled copper foil of Fig. 3 is { 200} on its rolling surface
CuThe crystal grain of planar orientation and { 220}
CuThere is the area ratio of roughly the same degree in the crystal grain of planar orientation.
On the other hand, the rolled copper foil of comparative example 1 shown in Figure 7 is with { 220}
CuDiffraction peak intensity I { the 220} of face
CuBe made as 100 occasion, { 200}
CuDiffraction peak intensity I { the 200} of face
CuBe 76, { 220}
CuThe crystal grain of planar orientation accounts for the advantage that overwhelms on the rolling surface of Copper Foil.In other words, mean as planting brilliant { 200}
CuThe crystal grain of planar orientation is considerably less.In taking all factors into consideration above-mentioned face orientation measure and 2 θ/θ measures as a result the time as can be known, in the rolled copper foil of embodiment 1, have copper crystal reliably as the 3 D tropism of the kind crystalline substance of formation cubes texture.With respect to this, in the rolled copper foil of comparative example 1, though have { 200} with respect to rolling surface
CuThe crystal grain of planar orientation, but orientation is very poor in their face, is indicating the kind crystalline substance that has 3 D tropism hardly.
[embodiment 2-3 and comparative example 2-3]
(annealing blank)
Four kinds of annealing blanks (before the final cold rolling process, thickness is 0.2mm and 0.1mm after the rough annealing) to making have as mentioned above carried out the XRD pole graph and have measured.Fig. 8 be to annealing blank rolling surface carried out { 220}
CuThe result's that the XRD pole graph of face is measured a example.Fig. 8 (a) is embodiment 2, and Fig. 8 (b) is embodiment 3, and Fig. 8 (c) is a comparative example 2, and Fig. 8 (d) is a comparative example 3.As indicated in Fig. 8, in whole samples in α=40-50
0Between have the maximum value Q of stdn intensity, in α=20-40
0Between have the mnm. S of stdn intensity.At this, when the ratio of getting maximum value Q and mnm. S was Q/S, as can be known, the value of embodiment 2 and embodiment 3 was respectively 2.2,2.6, and in the scope of " 2Q/S3 ", with respect to this, this value of comparative example 2 and comparative example 3 is respectively 3.1,1.5, outside above-mentioned scope.
(rolled copper foil in the final cold rolling process process)
Rolled copper foil in the final cold rolling process process of having used above-mentioned four kinds of blanks has been carried out the XRD pole graph to be measured.Fig. 9 is that the rolling surface to the rolled copper foil in the final cold rolling process process has carried out { 220}
CuThe result's that the XRD pole graph of face is measured a example.Fig. 9 (a) is embodiment 2, and Fig. 9 (b) is embodiment 3, and Fig. 9 (c) is a comparative example 2, and Fig. 9 (d) is a comparative example 3.
As indicated in Fig. 9, in each sample in α=25-35
0Between have the maximum value P (perhaps seeing its symptom of a trend) of stdn intensity, in α=40-50
0Between have the maximum value Q of stdn intensity, in α=85-90
0Between the increase of above-mentioned stdn intensity dullness.In addition, compare with Fig. 8 (a)-Fig. 8 (d) respectively, the stdn intensity of maximum value Q reduces thereupon.Such variation can think to come from the rolling rotation phenomenon that adds the copper crystal that man-hour, stress caused by above-mentioned.
(finishing the rolled copper foil of final cold rolling process)
The rolled copper foil of making as mentioned above (thickness is 16 μ m) of finishing rolling machining state (behind the final cold rolling process before the recrystallization annealing) has been carried out XRD determining.Figure 10 has carried out { 220} to the rolled copper foil of finishing final cold rolling process
CuThe result's that the XRD pole graph of face is measured a example.Figure 10 (a) is embodiment 2, and Figure 10 (b) is embodiment 3, and Figure 10 (c) is a comparative example 2, and Figure 10 (d) is a comparative example 3.
As indicated in Figure 10, there is the relation of " Q≤P≤R " in the rolled copper foil of embodiment 2 and embodiment 3, but the rolled copper foil of comparative example 2 then be " Q〉P, Q〉R ", the rolled copper foil of comparative example 3 is not almost detected maximum value Q.The relation of so-called " Q≤P≤R " can think that the kind crystalline substance of the interior cubes tissue that is orientated of the face of being meant exists with suitable amount, exists with essential enough amounts and accumulated processing strained rolling texture.With respect to this, the comparative example 3 that does not almost detect maximum value Q is indicating the kind crystalline substance that does not almost have the cubes tissue of orientation in the face.In addition, for " Q〉P, Q〉R " though comparative example 2 can think the kind crystalline substance that has the cubes tissue of orientation in the face, indicating that to have accumulated the formation of processing the strained rolling texture insufficient.
Figure 11 is an example that the above-mentioned rolled copper foil of finishing final cold rolling process has been carried out the result of 2 θ/θ mensuration.Figure 11 (a) is embodiment 2, and Figure 11 (b) is embodiment 3, and Figure 11 (c) is a comparative example 2.
As indicated in Figure 11, the rolled copper foil of embodiment 2 and embodiment 3 is presented at rolling surface and has a large amount of { 200}
CuThe crystal grain of planar orientation.With respect to this, there are a large amount of { 200} in the rolled copper foil of comparative example 2 at rolling surface
CuOn the other hand, also there are a large amount of { 111}C in the crystal grain of planar orientation
uThe crystal grain of planar orientation, but { 220}
CuThe crystal grain of planar orientation seldom.In addition, comparative example 3 obtains the result roughly the same with Fig. 7, becomes { the 200} of kind of crystalline substance
CuThe crystal grain of planar orientation is considerably less, { 220}
CuThe grains constitute advantage of planar orientation.
When take all factors into consideration that above-mentioned pole graph is measured and 2 θ/θ measures as a result the time as can be known, in the rolled copper foil of embodiment 2-3 with the remaining copper crystal grain that the brilliant 3 D tropism of kind that becomes the formation of cubes texture is arranged of suitable amount.With respect to this, be { 200} though the rolled copper foil of comparative example 3 exists rolling surface
CuThe crystal grain of planar orientation, but they all lack orientation in the face, are indicating the kind crystalline substance that has 3 D tropism hardly.In addition, in comparative example 2, can think, though { 200}C that can remaining really cubes tissue
uThe crystal grain of planar orientation, but it is insufficient to become the formation of " having accumulated processing strained rolling texture " of the motivating force that the cubes tissue forms.
[embodiment 1-3 and comparative example 1-3]
(rolled copper foil after the recrystallization annealing)
Each rolled copper foil (thickness is 16 μ m, finishes final cold rolling process) of making is as mentioned above being implemented to have carried out XRD determining after 60 minutes recrystallization annealings of 180 ℃ of insulations of temperature, par comprehensive orientation ratio [A] * [B] * [C].The result of the ratio [A] of table 3 expression cubes texture, table 4 presentation surface is orientated the result of orientation ratio [C] in ratio [B] and the face outward, the result of the comprehensive orientation of table 5 expression ratio [A] * [B] * [C].
In addition, as mentioned above, [A], [B], [C] calculate with following formula respectively.
The ratio of cubes texture [A]=I{200}
Cu/ (I{111}
Cu+ I{200}
Cu+ I{220}
Cu+ I{311}
Cu)
The face of cubes texture is orientated ratio [B]=Δ θ F outward
WHM/ Δ θ
IW
Orientation ratio [C]=Δ β in the face of cubes texture
FWHM/ Δ β
IW
Table 3 is with { 200}
CuThe diffracted intensity of face is 100 o'clock the relative intensity and the result of [A]
| {111} Cu | {200} Cu | {220} Cu | {311} Cu | [A] | |
| |
4 | 100 | 3 | 1 | 0.92 |
| |
2 | 100 | 3 | 1 | 0.94 |
| |
5 | 100 | 10 | 3 | 0.85 |
| Comparative example 1 | 5 | 100 | 5 | 4 | 0.88 |
| Comparative example 2 | 3 | 100 | 3 | 2 | 0.92 |
| Comparative example 3 | 10 | 100 | 35 | 9 | 0.65 |
The result of orientation ratio [C] in table 4 an outer orientation ratio [B] and the face
| Δθ FWHM | Δθ IW | [B] | Δβ FWHM | Δβ IW | [C] | |
| |
6.8 | 7.9 | 0.86 | 6.5 | 8.0 | 0.81 |
| |
7.4 | 7.7 | 0.96 | 7.0 | 7.5 | 0.93 |
| |
6.9 | 8.0 | 0.86 | 6.5 | 7.9 | 0.82 |
| Comparative example 1 | 6.9 | 9.4 | 0.73 | 6.7 | 9.1 | 0.74 |
| Comparative example 2 | 6.9 | 9.6 | 0.72 | 6.5 | 9.2 | 0.71 |
| Comparative example 3 | 6.7 | 9.5 | 0.71 | 7.1 | 9.6 | 0.76 |
The result of the comprehensive orientation of table 5 ratio [A] * [B] * [C]
| [A] | [B] | [C] | [A]×[B]×[C] | |
| |
0.92 | 0.86 | 0.81 | 0.64 |
| |
0.94 | 0.96 | 0.93 | 0.84 |
| |
0.85 | 0.86 | 0.82 | 0.60 |
| Comparative example 1 | 0.88 | 0.73 | 0.74 | 0.48 |
| Comparative example 2 | 0.92 | 0.72 | 0.71 | 0.47 |
| Comparative example 3 | 0.65 | 0.72 | 0.76 | 0.35 |
As indicated in the result of table 5, the rolled copper foil of embodiment 1-3 its comprehensive orientation ratio [A] * [B] * [C]
More much higher than 0.5, and its comprehensive orientation ratio of the rolled copper foil of comparative example 1-3 is lower than 0.5.This can think in finishing the rolled copper foil of final cold rolling process, comes from the copper crystal grain that whether has the brilliant 3 D tropism of kind that becomes the formation of cubes texture, and/or has accumulated the degree that processing strained rolling texture forms.
(curved characteristic of the rolled copper foil after the recrystallization annealing)
Following the carrying out of par to the curved characteristic of each rolled copper foil (embodiment 1-3 and comparative example 1-3, thickness are 16 μ m, after the recrystallization annealing) of making as mentioned above.Figure 12 has represented the schematic synoptic diagram of curved characteristic evaluation (slip pliability test).The slip bend test device uses Shinetsu Eng Co., Ltd.'s system, the device of model: SEK-31B2S, R=2.5mm, amplitude stroke=10mm, frequency=25Hz (amplitude speed=1500 time/minute), specimen width=12.5mm, specimen length=220mm is that rolling direction is measured with the length direction of coupons.Respectively 10 samples are measured.The results are shown in table 6.
The slip pliability test result of the rolled copper foil after table 6 recrystallization annealing
As indicated in the result of table 6, the rolled copper foil of embodiment 1-3 is compared the flex life number of times (high curved characteristic) that has more than 2 times with comparative example 1-3 as can be known.This result can think to come from the high comprehensive orientation ratio (with reference to table 5) of the cubes texture of embodiment 1-3.
Claims (13)
1. a rolled copper foil is the rolled copper foil before the recrystallization annealing behind final cold rolling process, it is characterized in that,
Measuring among the result obtain each 90 ± 5 ° { 220} that have the copper crystal that obtains by β scanning of α angle=45 that pole graph measures ° at least that have in the β angle by the X-ray diffraction pole graph that with the rolling surface is benchmark
CuThe face diffraction peak is also represented symmetric crystal grain 4 times.
2. rolled copper foil as claimed in claim 1 is characterized in that, represents that above-mentioned 4 symmetric diffraction peaks are with respect to the above-mentioned { 220} that is scanned the copper crystal that obtains by β
CuThe minimum strength of face diffraction has the diffracted intensity more than 1.5 times.
3. rolled copper foil as claimed in claim 1 or 2 is characterized in that,
Measuring by the X-ray diffraction pole graph that is benchmark among the result obtain, be transverse axis in the α angle of measuring with pole graph, with the rolling surface with the { 220} of the copper crystal that obtains by β scanning of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, the maximum value P that between α=25-35 °, has above-mentioned stdn intensity, the maximum value Q that between α=40-50 °, has above-mentioned stdn intensity, above-mentioned stdn intensity increases monotonously between α=85-90 °;
The value R of the above-mentioned stdn intensity of above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90 ° is " Q≤P≤R ".
4. rolled copper foil as claimed in claim 1 or 2 is characterized in that,
Measured among the result who obtains by the X-ray diffraction 2 θ/θ to the rolling face, the diffraction peak intensity of copper crystal is " I{200}
Cu〉=I{220}
Cu".
5. rolled copper foil as claimed in claim 3 is characterized in that,
Measured among the result who obtains by the X-ray diffraction 2 θ/θ to the rolling face, the diffraction peak intensity of copper crystal is " I{200}
Cu〉=I{220}
Cu".
6. a rolled copper foil is that any one described rolled copper foil in the claim 1,2,5 has been implemented the rolled copper foil after the recrystallization annealing, it is characterized in that,
From the ratio [A] of X-ray diffraction 2 θ of the rolling face/θ being measured the cubes texture of calculating, to the crystal grain of this cubes texture outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] and to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.
7. a rolled copper foil is that the described rolled copper foil of claim 3 has been implemented the rolled copper foil after the recrystallization annealing, it is characterized in that,
From the ratio [A] of X-ray diffraction 2 θ of the rolling face/θ being measured the cubes texture of calculating, to the crystal grain of this cubes texture outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] and to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.
8. a rolled copper foil is that the described rolled copper foil of claim 4 has been implemented the rolled copper foil after the recrystallization annealing, it is characterized in that,
From the ratio [A] of X-ray diffraction 2 θ of the rolling face/θ being measured the cubes texture of calculating, to the crystal grain of this cubes texture outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] and to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.
9. a rolled copper foil is to have implemented the rolled copper foil after the recrystallization annealing behind final cold rolling process, it is characterized in that,
From the ratio [A] of X-ray diffraction 2 θ of rolling surface/θ being measured the cubes texture of calculating, to the crystal grain of this cubes texture outside the X-ray diffraction swing curve is measured the face of calculating, be orientated ratio [B] and to the crystal grain of above-mentioned cubes texture from being that the X-ray diffraction pole graph of benchmark is measured be orientated ratio [C] in the face of calculating long-pending and is " [A] * [B] * [C] 〉=0.5 " with above-mentioned rolling surface.
10. the manufacture method of a rolled copper foil, the rolling surface that is the rolled copper foil before the recrystallization annealing after with final cold rolling process is being measured among the result obtain by the X-ray diffraction pole graph of benchmark, has { the 220} that there is the copper crystal that is obtained by β scanning of α angle=45 that pole graph measures ° in the β angle each 90 ± 5 °
CuThe face diffraction peak is also represented the manufacture method of the rolled copper foil of 4 symmetric crystal grain, it is characterized in that,
Behind above-mentioned final cold rolling process in the later rolling pass of second passage, comprise and have than one of the rolling pass of next-door neighbour's the big draught more than 1.1 times of last reduction in pass more than the passage.
11. the manufacture method of rolled copper foil as claimed in claim 10 is characterized in that,
The draught that a final passage in the above-mentioned final cold rolling process or a final preceding passage have an approximately maximum passage in the later rolling pass of second passage.
12. the manufacture method as claim 10 or 11 described rolled copper foils is characterized in that,
The total reduction of above-mentioned final cold rolling process is more than 80% below 90%.
13. the manufacture method of a rolled copper foil, the rolling surface of the rolled copper foil after with final cold rolling process before the recrystallization annealing is being measured among the result obtain by the X-ray diffraction pole graph of benchmark, each 90 ± 5 ° { 220} that have the copper crystal that is obtained by β scanning of α angle=45 that pole graph measures ° at least that have in the β angle
CuThe face diffraction peak is also represented symmetric crystal grain 4 times;
In the α angle of measuring with pole graph is transverse axis, with the copper crystal that obtains by β scanning of each α angle { the stdn intensity of 220}Cu face diffraction peak is that the longitudinal axis is when using curve representation, the maximum value P that between α=25-35 °, has above-mentioned stdn intensity, the maximum value Q that between α=40-50 °, has above-mentioned stdn intensity, above-mentioned stdn intensity increases monotonously between α=85-90 °; The value R of the above-mentioned stdn intensity of above-mentioned maximum value P and above-mentioned maximum value Q and above-mentioned α=90 ° is " Q≤P≤R "; It is characterized in that,
The rolling surface of the rolled copper foil after with rough annealing before the above-mentioned final cold rolling process is being measured among the result who obtains by the X-ray diffraction pole graph of benchmark, in the α angle of measuring with pole graph is transverse axis, with { the 220} of the copper crystal that is obtained by β scanning of each α angle
CuThe stdn intensity of face diffraction peak is that the longitudinal axis is when using curve representation, the maximum value Q that between α=40-50 °, has above-mentioned stdn intensity, the mnm. S that between α=20-40 °, has above-mentioned stdn intensity, the rolled copper foil that with the ratio of above-mentioned maximum value Q and above-mentioned mnm. S is " 2≤Q/S≤3 " is as the annealing blank;
The total reduction of above-mentioned final cold rolling process is more than 80% below 93%.
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| JP2008001069 | 2008-01-08 | ||
| JP2008-001069 | 2008-01-08 | ||
| JP2008001069 | 2008-01-08 | ||
| JP2008112476A JP5320638B2 (en) | 2008-01-08 | 2008-04-23 | Rolled copper foil and method for producing the same |
| JP2008112476 | 2008-04-23 | ||
| JP2008-112476 | 2008-04-23 |
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| CN101481760A true CN101481760A (en) | 2009-07-15 |
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| CN103255309A (en) * | 2012-02-17 | 2013-08-21 | 日立电线株式会社 | Rolled copper foil |
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2008
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5320638B2 (en) | 2013-10-23 |
| CN101481760B (en) | 2012-07-04 |
| JP2009185376A (en) | 2009-08-20 |
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