CN101168829A - Rolled copper foil and manufacturing method thereof - Google Patents

Abstract

A rolled copper foil applied with a recrystallization annealing after a final cold rolling step and having a crystal grain alignment satisfying a ratio of [a]/[b]>=3, where [a] and [b] are normalized average intensities of a {111}Cu plane diffraction of a copper crystal by beta-scanning at alpha=35 DEG and 74 DEG , respectively, in an X-ray diffraction pole figure measurement to a rolled surface is manufactured by controlling a total working ratio in the final cold rolling step before the recrystallization annealing to be 94% or more; and controlling a working ratio per one pass in the final cold rolling step to be 15 to 50%.

Description

Rolled copper foil and manufacture method thereof

Technical field

The present invention relates to rolled copper foil, relate in particular to the rolled copper foil and the manufacture method thereof that are suitable for the good curved characteristic of having of flexible distribution components such as flexible printed circuit board.

Background technology

Flexible printed circuit board (Flexible Printed Circuit is designated hereinafter simply as PFC) is owing to have thin thickness, a flexible excellent characteristic, thereby its degree of freedom to the installation form of electronics etc. is very high.Therefore, now, distribution of the moving part of the equipment of first-class moving part of the dogleg section of Collapsible mobile telephone, digital camera, printer and hard disk drive (HDD-Hard Disk Drive) and DVD (Digital Versatile Disk), CD relevant dishes such as (Compact Disk) etc. has all used FPC widely.

As the conductor of FPC, the general use carried out various surface-treated pure copper foil or copper alloy foil (below, abbreviate " Copper Foil " as).Copper Foil is divided into electrolytic copper foil and rolled copper foil two big classes according to the difference of its manufacture method.FPC requires to have good curved characteristic (for example, the curved characteristic more than 1,000,000 times) owing to being used as repeatedly the wiring material of moving part as mentioned above, uses the rolled copper foil person in the majority as Copper Foil.

Generally, the manufacture method of rolled copper foil is: after the ingot casting as raw-material reverberatory refining copper (JISH3100 C1100) or oxygen free copper (JIS H3100 C1020) is carried out hot rolling, through carrying out cold rolling and process annealing repeatedly up to preset thickness.The desired thickness of the rolled copper foil that FPC uses is generally below the 50 μ m, makes it further be thinned to the following tendency of tens μ m but have recently.

The manufacturing process of FPC briefly comprises: " FPC being pasted with the counterdie (base material) that resins such as Copper Foil and polyimide constitute; form the operation (CCL operation) of copper clad (CCL-Copper Claded Laminate) "; " on this CCL, form the operation of circuit layout by methods such as etchings ", " for the distribution on this circuit of protection carries out the surface-treated operation " etc.The CCL operation has following two kinds of methods: by means of binding agent with Copper Foil and base material lamination after, make adhesive cures and the tight method that connects (three layers of CCL) by thermal treatment, and do not use binding agent, to carry out after the surface-treated Copper Foil directly is fitted on the base material, through heating, pressure treatment and form the method for two layers of CCL of one.

Here, in the manufacturing process of FPC,, use Copper Foil after rolling processing (be in work hardening after hard state) from the viewpoint of the easiness made more.This is because if Copper Foil is in (soften) state after the annealing, during in the Copper Foil severing or with the base material lamination, is easy to generate the Copper Foil that forms defect ware and is out of shape (for example, extension, wrinkle, fracture etc.).

On the other hand, the curved characteristic of Copper Foil by recrystallization annealing after than significantly improving after the rolling processing.Therefore, for base material and Copper Foil in the above-mentioned CCL operation are fitted tightly in the thermal treatment that forms one, generally select the manufacture method of double band Copper Foil recrystallization annealing.In addition, heat-treat condition at this moment is for handling 1-60 minute (be typically 200 ℃ 30 minutes) at 180 ℃-300 ℃, and Copper Foil becomes the state of modified one-tenth recrystallized structure.

In order to improve the curved characteristic of FPC, the curved characteristic that improves as its raw-material rolled copper foil is effective.In addition, be well known that, usually, the curved characteristic of the Copper Foil after the recrystallization annealing, its cubes texture reaches good more all the more.In addition, generally said " prosperity of cubes texture " only be meant { 200} in rolling surface _CuThe occupation rate height of face (for example, more than 85%).

All the time, as the good rolled copper foil of curved characteristic, the following report is arranged: by (for example improving final rolling draught, more than 90%) and the Copper Foil that makes the method for cubes texture prosperity and stipulated the development degree of the cubes texture after the recrystallization annealing is (for example, rolling surface with X-ray diffraction try to achieve the intensity of 200} face is greater than the intensity of (200) face of trying to achieve with powder x-ray diffraction more than 20 times), stipulated Copper Foil thickness of slab direction perforation crystal grain ratio Copper Foil (for example, the section area rate is more than 40%), by (for example adding Copper Foil that trace additives controls softening temperature, control to 120 ℃-150 ℃ semi-softening temperature), stipulated that (for example, length surpasses the every 1mm of twin boundaries of 5 μ m for the Copper Foil of the length of twin boundaries ²The combined length of area be that 20mm is following), by (for example adding Copper Foil that trace additives controlled recrystallization texture, 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 below the 15 μ m) etc.(above these technology can be with reference to No. 3009383 communique of patent documentation 1-Japan special permission, patent documentation 2-TOHKEMY 2006-117977 communique, patent documentation 3-TOHKEMY 2000-212661 communique, patent documentation 4-TOHKEMY 2000-256765 communique, patent documentation 5-TOHKEMY 2001-323354 communique, patent documentation 6-TOHKEMY 2001-262296 communique, patent documentation 7-TOHKEMY 2005-68484 communique).

Yet highly integrated along with the miniaturization of electronics class in recent years, the progress of (to high-density install) and high performance etc. and is compared in the past, requires higher bending property to improve day by day to FPC.Because the curved characteristic of FPC is in fact by the curved characteristic decision of Copper Foil, thereby, the curved characteristic of Copper Foil must further be improved in order to meet the demands.

Summary of the invention

Therefore, the object of the present invention is to provide a kind of flexible distribution component that is applicable to flexible print circuit board (FPC) etc., and compare rolled copper foil in the past with good curved characteristic.Have again, a kind of manufacture method that can stably make the rolled copper foil with curved characteristic better than the past is provided.

The present inventor is by studying in great detail that the metallic crystal of cubes texture that the recrystallization annealing of relevant rolled copper foil is formed is learned, understood fully the preceding grain orientation state of recrystallization annealing, the particular kind of relationship that exists between grain orientation state after the recrystallization annealing and the curved characteristic has been finished the present invention in view of the above.

In order to realize the foregoing invention purpose, rolled copper foil provided by the invention is, behind final cold rolling process, carried out in the rolled copper foil of recrystallization annealing, it is characterized in that, resemble figure according to the X-ray diffraction utmost point that with the rolling surface is benchmark and measure the result obtain, the above-mentioned { 111} that scans at the β that establishes that the above-mentioned X-ray diffraction utmost point resembles that figure measures by α=35 ° and α=74 ° _CuWhen the stdn average intensity of the diffraction peak of face is respectively [a] and [b], have [a]/the grain orientation state of [b] 〉=3.

In addition, the feature of rolled copper foil provided by the invention is, according to measuring the result who obtains, { 111} by orientation in the X-ray diffraction face _CuFace is with respect to { the 200} of the rolling face _CuAverage (the ave-FWHM of the full width at half maximum (FWHM) of the diffraction peak of face _{{ 111}}) be below 10 °.

In addition, the feature of rolled copper foil provided by the invention is, measures the result who obtains according to the X-ray diffraction 2 θ/θ to the rolling face, the diffraction peak of copper crystal be above-mentioned { 200} more than 90% _CuFace; And, according to above-mentioned { 200} _CuThe X-ray diffraction rocking curve of face is measured the result who obtains, the full width at half maximum (FWHM) (FWHM of this diffraction peak _{{ 200}}) be below 10 °.

In addition, the feature of rolled copper foil provided by the invention is, measures the result who obtains according to the X-ray diffraction 2 θ/θ to the rolling face, the diffraction peak of copper crystal be above-mentioned { 200} more than 90% _CuFace; And, according to above-mentioned { 200} _CuThe X-ray diffraction rocking curve of face is measured the result who obtains, the full width at half maximum (FWHM) (FWHM of this diffraction peak _{{ 200}}) and integral breadth (IW _{{ 200}}) ratio be 0.85≤IW _{{ 200}}/ FWHM _{{ 200}}≤ 1.15; And, measure the result who obtains according to resemble figure by the X-ray diffraction utmost point that with above-mentioned rolling surface is benchmark, the grain orientation state that has is: at above-mentioned { 111} _CuFace is with respect to above-mentioned { 200} _CuIn 4 asymmetrical diffraction peak values of face, the full width at half maximum (FWHM) (FWHM of any one diffraction peak _{{ 111}}) and integral breadth (IW _{{ 111}}) ratio be 0.85≤IW _{{ 111}}/ FWHM _{{ 111}}≤ 1.15.

In addition, the feature of rolled copper foil provided by the invention is, is more than the 40 μ m in the median size of viewed this recrystal grain on the rolling face.

In addition, the feature of rolled copper foil provided by the invention is, comprises the Sn of 0.001-0.009 quality % in the copper alloy that uses as rolled copper foil, and all the other are Cu and unavoidable impurities.

In order to realize the foregoing invention purpose, rolled copper foil provided by the invention is in the rolled copper foil behind final cold rolling process before the recrystallization annealing, to it is characterized in that, measure the result who obtains according to resemble figure by the X-ray diffraction utmost point that with the rolling surface is benchmark, at { the 111} that will obtain by the β scanning of each α angle _CuWhen the stdn average intensity of the diffraction peak of face plotted curve, the grain orientation state that has was: above-mentioned α angle is that the above-mentioned stdn average intensity of 35 ° of-75 ° of scopes is non-stepped, perhaps, in fact only has a greatly zone.

In addition, the feature of rolled copper foil provided by the invention is, measures the result who obtains according to the X-ray diffraction 2 θ/θ to rolling surface, the diffraction peak of copper crystal be { 200} more than 80% _CuFace.

In addition, the feature of rolled copper foil provided by the invention is, comprises the Sn of 0.001-0.009 quality % in the copper alloy that uses as rolled copper foil, and all the other are Cu and unavoidable impurities.

In order to realize the foregoing invention purpose, the manufacture method of rolled copper foil provided by the invention is, in the rolled copper foil behind final cold rolling process before the recrystallization annealing, the Copper Foil of manufacturing resembles figure according to the X-ray diffraction utmost point that with the rolling surface is benchmark and measures the result who obtains, at { the 111} that will be obtained by the β scanning of each α angle _CuWhen the stdn average intensity of the diffraction peak of face plotted curve, above-mentioned α angle was that the above-mentioned stdn average intensity of 35 ° of-75 ° of scopes is non-stepped, perhaps, in fact only had a greatly zone; It is characterized in that, the total reduction of the final cold rolling process before the recrystallization annealing is decided to be more than 94%, and the draught in each road is controlled at 15-50%.

In addition, the feature of the manufacture method of rolled copper foil provided by the invention is, in the final cold rolling process before recrystallization annealing, control the draught that the rolling draught in each road makes draught 〉=the 3rd road in draught 〉=second road of winning, and the later draught in per three roads is controlled at 15-25%.

According to the present invention, a kind of flexible distribution component that is applicable to flexible print circuit board (FPC) etc. can be provided, and compare rolled copper foil in the past with good curved characteristic.In addition, can provide a kind of manufacture method that can stably make rolled copper foil with curved characteristic better than the past.

Description of drawings

Fig. 1 is the synoptic diagram of the oikocryst face of expression copper crystal.

Fig. 2 is the sketch of mutual relationship of incident X-rays, detector, sample, the scan axis of expression X-ray diffraction.

Fig. 3 is the rolled copper foil for present embodiment, is carrying out under the state of recrystallization annealing behind final cold rolling process, by being { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles the example that figure measures the result who obtains.

Fig. 4 is the rolled copper foil for present embodiment, has carried out having carried out { the 200} with respect to rolling surface under the state of recrystallization annealing behind final cold rolling process _CuThere is { the 111} of the position relation of 55 ° (according to condition determinations, α=35 °) in face _CuThe result's that orientation is measured in the XRD face of face a example.

Fig. 5 is the rolled copper foil for present embodiment, has carried out under the state of recrystallization annealing behind final cold rolling process, rolling surface has been carried out X-ray diffraction 2 θ/result's that θ mensuration obtains a example.

Fig. 6 is the rolled copper foil for present embodiment, has carried out under the state of recrystallization annealing rolling surface having been carried out { 200} behind final cold rolling process _CuThe result's that the XRD rocking curve of face (single crystal X diffracted intensity distribution curve) is measured a example.

Fig. 7 is the rolled copper foil for present embodiment, behind the final cold rolling process and under the state before recrystallization annealing, by being { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles the example that figure measures the result who obtains.

Fig. 8 is the rolled copper foil for present embodiment, behind the final cold rolling process and under the state before recrystallization annealing, rolling surface has been carried out X-ray diffraction 2 θ/result's that θ mensuration obtains a example.

Fig. 9 is the whole schema of manufacturing process of the rolled copper foil of expression embodiments of the present invention.

Figure 10 is an example of X-ray diffraction 2 θ to the rolling surface/θ measurement result behind final cold rolling process and before recrystallization annealing.Figure 10 (a) is embodiment 1, and Figure 10 (b) is a comparative example 1, and Figure 10 (c) is a comparative example 2, and Figure 10 (d) is a comparative example 3.

Figure 11 be embodiment 1 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 11 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 11 (b) represented is that positive pole resembles figure.

Figure 12 be comparative example 1 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 12 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 12 (b) represented is that positive pole resembles figure.

Figure 13 be comparative example 2 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 13 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 13 (b) represented is that positive pole resembles figure.

Figure 14 be comparative example 3 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 14 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 14 (b) represented is that positive pole resembles figure.

Figure 15 is the example of graphic representation of the stdn average intensity of embodiment 1.

Figure 16 is the example of graphic representation of the stdn average intensity of comparative example 3.

Figure 17 is the synoptic diagram of the summary of expression curved characteristic evaluation (slip pliability test).

Figure 18 be comparative example 4 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 18 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 18 (b) represented is that positive pole resembles figure.

Embodiment

What Fig. 1 represented is the synoptic diagram of the relevant main crystal face of copper crystal of the present invention of expression.Because the crystalline structure of copper is a cubic system, there are following relation in each crystal face and face direction:

{ 111} _CuFace and { 100} _CuThe angle that face forms is 55 °,

{ 111} _CuFace and { 110} _CuThe angle that face forms is 35 °,

{ 111} _CuFace and { 112} _CuThe angle that face forms is 90 °,

{ 111} _CuFace and＜112 〉 _CuThe face direction is parallel.

{ } presentation surface wherein,＜the presentation surface direction.

Fig. 2 is the sketch of relation of incident X-rays, detector, sample, the scan axis of expression X-ray diffraction (below, the situation that is expressed as XRD is also arranged).Below, use Fig. 2 illustrates the evaluation method about the grain orientation state of the rolled copper foil that utilizes XRD.In addition, three scan axises among Fig. 2 generally are called the sample axle with the θ axle, and the α axle is called door-hinge, and the β axle is called the rotating shaft of face inward turning.In addition, X-ray diffraction of the present invention is all undertaken by CuK α line.

With respect to incident X-rays, with the θ axle sample and detector are scanned, be θ with the sweep angle of sample, the sweep angle of detector is that measuring method that 2 θ scan is called 2 θ/θ and measures.Measure by 2 θ/θ, on the vertical direction of sample face (the present invention is a rolling surface) that is multicrystal rolled copper foil, can estimate which crystal face take advantage (occupation rate of rolling surface).

With regard to some diffraction surfaces { hkl} _Cu, for { the hkl} of indication _Cu2 θ values of face (sweep angle 2 θ of fixed detector) are called rocking curve with the measuring method that only sample is carried out the scanning of θ axle and measure.{ the hkl} that obtains with this mensuration _CuFull width at half maximum (FWHM) (the FWHM of face peak value _{{ hkl}}) or integral breadth (IW _{{ hkl}}) can estimate { hkl} _CuThe orientation degree of the rolling surface vertical direction of face.At this moment, we can say full width at half maximum (FWHM) (FWHM _{{ hkl}}) or integral breadth (IW _{{ hkl}}) value more little, just good more perpendicular to the crystalline orientation of rolling surface direction.In other words, because the crystalline structure of copper is a cubic system, thereby, can think full width at half maximum (FWHM) (FWHM _{{ hkl}}) or integral breadth (IW _{{ hkl}}) show the offsetting dip of the vertical direction of the relative rolling surface of cubes with which kind of degree.In addition, full width at half maximum (FWHM) (FWHM _{{ hkl}}) be defined as the spike width of a half intensity of diffraction peak intensity, integral breadth (IW _{{ hkl}}) be defined as the value of removing the integrated intensity of diffraction peak with the maximum strength of this diffraction peak.

With regard to some diffraction surfaces { hkl} _Cu, for { the hkl} of indication _Cu2 θ values of face (sweep angle 2 θ of fixed detector) are carried out α axle scanning with stepped start-stop system, will be called the utmost point to the measuring method that each α value is carried out the β scanning (from 0 ° to 360 ° in face internal rotation (rotation)) of sample and resemble figure mensuration.By this mensuration, can estimate { the hkl} of indication _CuFace is from the degree of the vertical direction inclination of rolling surface.

In addition, resemble in the figure mensuration, will be defined as α=90 ° also conduct mensuration benchmark with the vertical direction of sample face at the XRD utmost point of the present invention.In addition, measure reflection method is arranged two kinds of (α=15 °-90 °) and transmission methods (α=0 °-15 °) though the utmost point resembles figure, the utmost point of the present invention resembles figure and measures with reflection method (α=15 °-90 °) and measure.

Utilized one of evaluation method that the utmost point resembles the feature that figure measures to have in the face orientation measure.This measuring method is: will with indication { hkl} _CuThe crystal face of face geometry correspondence { h ' k ' l ' } _CuFace and this { hkl} _CuThe angle that face constitutes is made as α ' time, carries out α axle scanning (sample is tilted) in " α=90 °-α ' " mode, for h ' k ' l] } _Cu2 θ values of face (sweep angle 2 θ of detector are fixed) are carried out β scanning (0 ° to 360 ° face internal rotation (rotation)) to sample.Full width at half maximum (FWHM) (the FWHM of { h ' k ' l ' } the face peak value that obtains with this mensuration _{{ h ' k ' l ' }}) or integral breadth (IW _{{ h ' k ' l ' }}) can estimate { h ' k ' l ' } _CuTwo axial orientation degree in the rolling surface of face.At this moment, we can say full width at half maximum (FWHM) (FWHM _{{ h ' k ' l ' }}) or integral breadth (IW _{{ h ' k ' l ' }}) value more little, the crystalline orientation degree of direction is good more in the rolling surface.In other words, can think full width at half maximum (FWHM) (FWHM _{{ h ' k ' l ' }}) or integral breadth (IW _{{ h ' k ' l ' }}) show cubes offset rotation (departing from) with which kind of degree in rolling surface from " checker " shape.In addition, same as described above, full width at half maximum (FWHM) (FWHM _{{ h ' k ' l ' }}) be defined as the spike width of a half intensity of diffraction peak intensity, integral breadth (IW _{{ h ' k ' l ' }}) be defined as the value of removing the integrated intensity of diffraction peak with the maximum strength of this diffraction peak.Have again, as if { h ' k ' l ' } that this mensuration is obtained _CuThe full width at half maximum (FWHM) of face peak value on average be defined as (ave-FWHM _{{ h ' k ' l ' }}), then can use (ave-FWHM _{{ h ' k ' l ' }}) evaluation { h ' k ' l ' } _CuTwo axial orientation degree in the rolling surface of face.At this moment, we can say (ave-FWHM _{{ h ' k ' l ' }}) value is more little, then the crystalline orientation degree of direction is good more in the rolling surface.In other words, can think (ave-FWHM _{{ h ' k ' l ＇ }}) show cubes offset rotation (departing from) with which kind of degree in rolling surface from " checker " shape.First embodiment of the present invention

At first, description standard average intensity ratio.

The feature of the rolled copper foil of present embodiment is: carrying out under the state of recrystallization annealing behind final cold rolling process, is the above-mentioned { 111} that the β scanning by α=35 ° that the X-ray diffraction utmost point of benchmark resembles that figure measures obtains with the rolling surface _CuThe stdn average intensity [a] of the diffraction peak of face and the above-mentioned { 111} that obtains by the β scanning of α=74 ° _CuThe ratio of the stdn average intensity [b] of the diffraction peak of face is [a]/[b] 〉=3.

At this, so-called stdn average intensity Rc is meant at the XRD utmost point and resembles during figure measures, the set { hkl} that the β scanning (face inward turning rotating shaft scanning) of each α angle is obtained _CuDiffraction peak intensity equalization counting, can calculate by following formula (details with reference to following document).In addition, the logical conventional computer of standardized calculating is implemented.

Rc＝Ic/Istd

Wherein,

Ic: corrected strength (background correction absorbs and revises)

Istd: the intensity that the stdn of being tried to achieve by calculating is used

Document name: " RAD system software textile analysis Program Operation Description book (specification sheets numbering: MJ201RE) ", Rigaku Denki Co., Ltd, P22-23.

Document name: " the anodal point operation specification sheets of CN9258E101 RINT2000 serial application software (specification sheets numbering: MJ10102A01) ", Rigaku Denki Co., Ltd, P8-10.

In addition, the reason that the stdn of XRD peak strength is used is, the different influences that bring of condition enactments such as the tube voltage in order to eliminate because of XRD determining and tube current can compare (in fact then not installing dependency).

On the other hand, { 111} _Cu{ the 200} to rolling surface of face _CuThe stdn average intensity [b] that the XRD utmost point of face resembles the stdn average intensity [a] of α=35 that figure measures ° and α=74 ° has following meaning respectively.

As mentioned above, because { 111} _Cu{ the 200} to rolling surface of face _CuThe angle that face forms is being 55 ° geometrically, thereby α=35 ° (=90 °-55 °).Stdn average intensity [a] and rolling surface { 200} _Cu{ the 111} of face correspondence _CuThe diffracted intensity of face.In other words, be meant { the 200} of rolling surface _CuThe normalized diffracted intensity of face.

Similarly, { the 200} of rolling surface _CuFace and { 111} _CuIn the face of being somebody's turn to do { 200} _CuThe angle that the twin crystal zone of face forms is being 16 ° geometrically, thereby α=74 ° (=90 °-16 °).Stdn average intensity [b] and rolling surface { 200} _CuCorresponding { the 111} in twin crystal zone of face _CuThe diffracted intensity of face.In other words, be meant { 200} to rolling surface _CuThe twin crystal regional standard change of face diffracted intensity.

Therefore, [a]/[b] is meant { 200} as cubes texture of rolling surface _CuThe normalized diffracted intensity ratio of face and crystalline region with this twin crystal relation.

Fig. 3 is the rolled copper foil for present embodiment, is carrying out under the state of recrystallization annealing behind final cold rolling process, by being { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles the example that figure measures the result who obtains.As indicated in Fig. 3, { the 111} of α=35 ° _CuThe ratio of the stdn average intensity [b] of the stdn average intensity [a] of face and α=74 ° is [a]/[b] 〉=3.This result shows, at { 200} _CuFace is in the cubes texture of main body, is { 200} _CuThe few rolled copper foil of the twin crystal tissue of face (twin crystal zone).

On the other hand, if the stdn average intensity then can not obtain the curved characteristic higher than the past than for [a]/[b]＜3.Therefore, get [a]/[b] 〉=3.Preferably [a]/[b] 〉=3.5.More preferably [a]/[b] 〉=4.Second embodiment of the present invention

Secondly, orientation is measured in the explanation face.

Except the feature of first embodiment of the present invention, the feature of the rolled copper foil of present embodiment is: carried out under the state of recrystallization annealing behind final cold rolling process, according to { the 200} with respect to cubes texture _CuThere is { the 111} of 55 ° of position relations in face _CuThe full width at half maximum (FWHM) FWHM that orientation is measured in the XRD face of face _{{ 111}}Be below 10 °.

Fig. 4 is the rolled copper foil for present embodiment, has carried out having carried out { the 200} with respect to rolling surface under the state of recrystallization annealing behind final cold rolling process _CuThere is { the 111} of the position relation of 55 ° (according to condition determinations, α=35 °) in face _CuThe result's that orientation is measured in the XRD face of face a example.As indicated in Fig. 4, presented 4 peak values, promptly (when rolling direction was decided to be β=0 °, the center of each peak value for example was respectively: 45 °, 135 °, 225 °, 315 ° of β ≌) for 4 symmetric diffraction peaks.If cubes texture is very flourishing (for example, if { the 200} of recrystal grain _CuFace occupies the about more than 90% of rolling surface), then except above-mentioned 4 peak values, nearly all undetected by β scanning.In addition, according to { 111} _Cu(the ave-FWHM that orientation is measured in the face of face _{{ 111}}) be (4 peak value is average) below 10 °.This result represents { 111} _CuFace is the rolled copper foil that direction has good orientation (having good degree of grain alignment) in rolling surface.

On the other hand, if { 111} _Cu(the ave-FWHM of face _{{ 111}}) surpassing 10 °, then can not obtain than existing high curved characteristic.Therefore, (ave-FWHM _{{ 111}}) get below 10 °.Be preferably below 9.5 °.More preferably below 9 °.

The 3rd embodiment of the present invention

Then, illustrate that 2 θ/θ measures.

Except the feature of first embodiment of the present invention, the feature of the rolled copper foil of present embodiment is: the rolling Copper Foil is being carried out under the state after the recrystallization annealing, and rolling surface is at { the 200} of this recrystal grain _CuHave on the face take by force to, its occupation rate is more than 90%.

Fig. 5 is the rolled copper foil for present embodiment, behind final cold rolling process and carried out under the state of recrystallization annealing, rolling surface has been carried out the example that X-ray diffraction 2 θ/θ measures the result who obtains.As indicated in Fig. 5, rolling surface is at { the 200} of this recrystal grain _CuHave on the face and take by force to, { 220} _CuThe occupation rate of face is more than 90%.This demonstrates is the very flourishing rolled copper foil of cubes texture.

On the other hand, if { 220} _CuThe occupation rate less than 90% of face then can not obtain than existing high curved characteristic.Therefore, { 220} _CuThe occupation rate of face is got more than 90%.Be preferably more than 92%.More preferably more than 94%.

In addition, above-mentioned { 220} _CuThe occupation rate of face is defined as follows:

{ 220} _CuThe occupation rate of face (%)=[I{220} _Cu/ (I{111} _Cu+ I{200} _Cu+ I{220} _Cu+ I{311} _Cu)] * 100

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 mensuration of rocking curve then, is described.

Except above-mentioned feature, the additional features of the rolled copper foil of present embodiment is: the rolling Copper Foil is being carried out under the state after the recrystallization annealing, rolling surface have take by force to { 200} _CuFace is measured the full width at half maximum (FWHM) { FWHM of the diffraction peak that obtains by rocking curve _{{ 200}}) below 10 °.

The present invention is conceived to account for { the 200} of the recrystal grain of above-mentioned rolling surface more than 90% _CuThe diffracted ray of face is estimated { 200} _CuThe degree of grain alignment of face.Fig. 6 is the rolled copper foil for present embodiment, behind final cold rolling process and carried out under the state of recrystallization annealing, rolling surface has been carried out the result's that the XRD rocking curve measures a example.As indicated in Fig. 6, { 200} _CuFace measure the full width at half maximum (FWHM) (FWHM of the diffraction peak obtain by rocking curve _{{ 200}}) below 10 °.This result shows that it is { 200} _CuFace has the rolled copper foil of good orientation (having good degree of grain alignment) in the vertical direction of rolling surface.

On the other hand, if { 200} _CuFull width at half maximum (FWHM) (the FWHM of the diffraction peak of face _{{ 200}}) surpassing 10 °, then can not obtain than existing high curved characteristic.Therefore, the full width at half maximum (FWHM) (FWHM of the rolling surface of rolled copper foil _{{ 200}}) be decided to be below 10 °.Preferred below 9.5 °, more preferably below 9 °.

The 4th embodiment of the present invention

The mensuration of rocking curve then, is described.

Except the feature of first embodiment of the present invention, the feature of the rolled copper foil of present embodiment is: behind final cold rolling process, carrying out under the state of recrystallization annealing, according to rolling surface have take by force to { 200} _CuFace is measured the result who obtains, the full width at half maximum (FWHM) (FWHM of this diffraction peak by rocking curve _{{ 200}}) and integral breadth (IW _{{ 200}}) ratio be 0.85≤IW _{{ 200}}/ FWHM _{{ 200}}≤ 1.15.

The present invention is conceived to account for { the 200} of the recrystal grain of above-mentioned rolling surface more than 90% _CuThe diffracted ray of face is as { 200} _CuThe degree of grain alignment of face is estimated full width at half maximum (FWHM) (FWHM _{{ 200}}) and integral breadth (IW _{{ 200}}) the ratio.Full width at half maximum (FWHM) (FWHM _{{ 200}}) and integral breadth (IW _{{ 200}}) ratio be more than 0.85, below 1.15, i.e. full width at half maximum (FWHM) (FWHM _{{ 200}}) and integral breadth (IW _{{ 200}}) value roughly the same be the few shape of diffraction peak hangover, be meant the high meaning of ratio of the crystal grain in orientation with crystal orientation amplitude of fluctuation little (inclination angle is departed from minimum).For example, the shape of diffraction peak approaches trapezoidal or rectangle, then FWHM more _{{ 200}}And IW _{{ 200}}Ratio (FWHM _{{ 200}}/ IW _{{ 200}}) approach 1 more.

On the other hand, if { 200} _Cu(the FWHM of face _{{ 200}}) and (IW _{{ 200}}) ratio (IW _{{ 200}}/ FWHM _{{ 200}}) less than 0.85 or above 1.15, then can not obtain than existing high curved characteristic.Therefore, this ratio is taken as more than 0.85, below 1.15.More preferably more than 0.9, below 1.1.In addition, from grain-oriented viewpoint, much less, with FWHM _{{ 200}}And IW _{{ 200}}Absolute value less for well.For example, for FWHM _{{ 200}}, with better, preferred below 9.5 ° below 10 °, more preferably below 9 °.

Then, orientation is measured in the explanation face.

Except above-mentioned feature, the additional features of the rolled copper foil of present embodiment is: behind final cold rolling process, carrying out under the state of recrystallization annealing, on rolling surface relatively, have take by force to { 200} _CuThere is { the 111} of 55 ° of position relations in face _CuFace measure in the four subsymmetric diffraction peaks obtain the full width at half maximum (FWHM) (FWHM of any one diffraction peak by orientation in the XRD face _{{ 111}}) and integral breadth (IW _{{ 111}}) ratio be 0.85≤IW _{{ 111}}/ FWHM _{{ 111}}≤ 1.15.

The present invention has carried out being conceived to { the 200} of relative rolling surface under the state of recrystallization annealing behind final cold rolling process _CuThere is { the 111} of 55 ° of (according to condition determination, α=35 °) position relations in face _CuThe diffracted ray of face is as { 111} _CuOrientation degree is estimated full width at half maximum (FWHM) (FWHM in the face of face _{{ 111}}) and integral breadth (IW _{{ 111}}) the ratio.In addition, because { 200} _CuFace and { 100} _CuFace is parallel, thereby { 200} _CuFace and { 111} _CuYes 55 ° (with reference to Fig. 1) for the angle that face constitutes.

{ the 200} that is oriented to owing to rolling surface _CuFace is if measure { 111} _CuThe face diffraction then presents four peak values, and promptly (when rolling direction was decided to be 0 ° of β ≌, the center of each peak value for example was respectively: 45 °, 135 °, 225 °, 315 ° of β ≌) for 4 symmetric diffraction peaks.As long as { the 200} of recrystal grain _CuFace accounts for the about more than 90% of rolling surface, removes above-mentioned four peak values and scans the peak value that almost detects less than other with external application β.

With above-mentioned same, full width at half maximum (FWHM) (FWHM _{{ 111}}) and integral breadth (IW _{{ 111}}) ratio be more than 0.85, below 1.15, i.e. full width at half maximum (FWHM) (FWHM _{{ 111}}) and integral breadth (IW _{{ 111}}) value roughly the same be the few shape of diffraction peak hangover, be meant the high meaning of ratio of the crystal grain in orientation with crystal orientation amplitude of fluctuation little (inclination angle is departed from minimum).For example, the shape of diffraction peak approaches trapezoidal or rectangle, then FWHM more _{{ 111}}And IW _{{ 111}}Ratio (IW _{{ 111}}/ FWHM _{{ 111}}) approach 1 more.

On the other hand, if { 111} _Cu(the FWHM of face _{{ 111}}) and (IW _{{ 111}}) ratio (IW _{{ 111}}/ FWHM _{{ 111}}) less than 0.85 or above 1.15, then can not obtain than existing high curved characteristic.Therefore, this ratio is taken as more than 0.85, below 1.15.More preferably more than 0.9, below 1.1.In addition, from grain-oriented viewpoint, much less, with FWHM _{{ 111}}And IW _{{ 111}}Absolute value less for well.For example, for FWHM _{{ 111}}, with better, preferred below 9.5 ° below 10 °, more preferably below 9 °.

Conclude grain orientation state so far.The rolled copper foil of embodiments of the present invention at first, behind the final cold rolling process and under the state before recrystallization annealing, has formed good the rolling texture ({ 220} more than 80% _CuThe occupation rate of face and suppressed recrystallize phenomenon in the cold rolling course of processing).In addition, this rolled copper foil is being carried out under the state of recrystallization annealing { 200} _CuThe occupation rate of face is more than 90%, should { 200} _CuThe amplitude of fluctuation of face is very little, and has formed { 111} _CuThe cubes texture that the amplitude of fluctuation of face is very little.This can think that there is the state (grain orientation state) of three-dimensional good proper alignment in the cubic system of copper.

Then, the mechanism that realizes high curved characteristic is described.

Below, the mechanism of the high curved characteristic of realization of the rolled copper foil of embodiments of the present invention is described simply.

When to the Metallic Solids stress application, though dislocation moves along the crystalline slip plane easily, the grain boundary generally becomes the obstacle to dislocation moving.In as multicrystal rolled copper foil, if because the bending motion dislocation accumulates in grain boundary etc. locates, then be easy to generate crackle assembling part, can think to have caused so-called metal fatigue.If get opposite view,, then can realize the raising of curved characteristic as long as can suppress the gathering of dislocation in polycrystal.

As mentioned above, the rolled copper foil of embodiments of the present invention (behind final cold rolling process, having carried out under the state of recrystallization annealing), because the cubic system of copper has the crystal structure of three-dimensional good proper alignment, thereby can think that when bending is transported to dislocation causes that the probability of cross slip is very high.Therefore, can think that grain boundary etc. is difficult to become the obstacle to dislocation moving, curved characteristic can improve (flex life is prolonged often).

In other words, in order to cause cross slip effectively, need to make { 200} at least _CuThe occupation rate height of face makes this { 200} _CuThe amplitude of fluctuation of face is little, and { 111} _CuThe amplitude of fluctuation of face is also little, i.e. three all good (for example, { 200} of orientation _CuThe occupation rate of face 〉=90%, 0.85≤IW _{{ 200}}/ FWHM _{{ 200}}≤ 1.15 and 0.85≤IW _{{ 111}}/ FWHM _{{ 111}}≤ 1.15).

Its reason be because, even so-called cubes texture is done to such an extent that very flourishingly (usually refer to { 200} _CuThe high state of occupation rate in the face of rolling surface), if { 200} _CuFace and { 111} _CuThe amplitude of fluctuation of face is not little, then is easy to generate big skew in adjacent intercrystalline slip direction, is difficult to cause cross slip.

The 5th embodiment of the present invention

The median size of the recrystal grain of rolled copper foil then, is described.

The feature of the rolled copper foil of present embodiment is: carried out under the state of recrystallization annealing behind final cold rolling process, the median size of observing this recrystal grain of rolling surface is more than the 40 μ m.

As mentioned above, in polycrystal,, just can realize the raising of curved characteristic as long as can suppress the accumulation (perhaps, preventing the obstacle of dislocation moving) of dislocation.That is, the cubic system of copper by the particle diameter (grain boundary itself is reduced) that strengthens recrystal grain, then improves the more remarkable effect of curved characteristic except being the grain orientation state of three-dimensional proper alignment.

But even reduce the grain boundary, if three orientations of recrystal grain are low, the effect that improves curved characteristic is also very little.That is, the rolled copper foil of present embodiment has dislocation and causes that the grain orientation of cross slip and so on also is a precondition when bending is transported to.In addition, for the median size of recrystal grain being made more than the 40 μ m, can be by when increasing the total reduction (for example, more than 94%) of final cold rolling process, the recrystallize phenomenon (details will in aftermentioned) that suppresses in the cold rolling course of processing realizes.

On the other hand, if the median size of recrystal grain is littler than 40 μ m, then can not obtain than existing high curved characteristic.Therefore, the median size of recrystal grain is got more than the 40 μ m.More than the preferred 50 μ m, more preferably more than the 60 μ m.

The 6th embodiment of the present invention

Then, description standard average intensity.

The feature of the rolled copper foil of present embodiment is: behind the final cold rolling process and under the state before recrystallization annealing, be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles in the figure mensuration, and the stdn average intensity of α angle in 35 ° of-75 ° of scopes is non-stepped, and perhaps greatly in fact only there is one in the zone.

Fig. 7 is the rolled copper foil for present embodiment, behind the final cold rolling process and under the state before recrystallization annealing, by being { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles the example that figure measures the result who obtains.As indicated in Fig. 7, demonstrate in α=35 in °-75 ° the scope and be { 111} _CuThe stdn average intensity of face is non-stepped, perhaps has the rolled copper foil that in fact only there is one grain orientation state in very big zone.This shows that the recrystallize phenomenon in the cold rolling course of processing is suppressed, and has formed good rolling texture.

On the other hand, { the 111} in the scope of α=35 °-75 ° _CuIf the stdn average intensity of face is stepped, if there is the rolled copper foil of a plurality of grain orientation states in perhaps very big zone, carrying out in the rolled copper foil of recrystallization annealing thereafter, then can not obtain the curved characteristic higher than the past.Therefore, make { 111} in the scope of α=35 °-75 ° _CuThe stdn average intensity of face is non-stepped, perhaps has the rolled copper foil that in fact only there is one grain orientation state in very big zone.

The 7th embodiment of the present invention

Then, illustrate that 2 θ/θ measures.

The feature of the rolled copper foil of present embodiment is: under the state behind final cold rolling process before the recrystallization annealing, and { the 200} of copper crystal _CuFace on rolling surface, have take by force to, its occupation rate is more than 80%.

Fig. 8 is the rolled copper foil for present embodiment, behind the final cold rolling process and under the state before recrystallization annealing, rolling surface has been carried out X-ray diffraction 2 θ/result's that θ mensuration obtains a example.As indicated in Fig. 8, rolling surface is oriented to { 220} by force _CuFace should { 220} _CuThe occupation rate of face is more than 80%.This expression is the rolled copper foil that has formed good rolling texture.

On the other hand, if { 220} _CuThe occupation rate less than 80% of face can not obtain in the rolled copper foil that has carried out recrystallization annealing thereafter than existing high curved characteristic.Therefore, { 220} _CuThe occupation rate of face is got more than 80%.Be preferably more than 85%.More preferably more than 90%.

In addition, above-mentioned { 220} _CuThe occupation rate of face is defined as follows:

{ 220} _CuThe occupation rate of face (%)=[I{220} _Cu/ (I{111} _Cu+ I{200} _Cu+ I{220} _Cu+ I{311} _Cu)] * 100

The 8th embodiment of the present invention

Then, the copper alloy that rolled copper foil is described is formed.

The FPC of present embodiment is that by the Sn that comprises 0.001-0.009 quality %, all the other are the copper alloy that copper and unavoidable impurities constitute with the feature of rolled copper foil.

In the present embodiment, the qualification reason specification sheets of the interpolation reason of the alloying constituent of the copper alloy of formation FPC usefulness rolled copper foil and content is as follows.

In rolled copper foil, the total reduction big more (for example, more than 90%) of final cold rolling process then has to cause normal temperature remollescent tendency easily.When causing this undesirable phenomenon (normal temperature softening), the then severing of the Copper Foil in FPC manufacturing process and be easy to generate the distortion of Copper Foil during with the lamination of base material becomes the reason that yield rate reduces.

By in copper, containing Sn,, also can suppress normal temperature softening (control softening temperature and recrystallize begin temperature) even carried out strong processing at final cold rolling process.In addition, said here " normal temperature softening " has comprised the recrystallize phenomenon (details will in aftermentioned) of the part in the cold rolling processing.Be accompanied by the increase that contains the Sn amount, the softening temperature of rolled copper foil rises.Be less than the occasion of 0.001 quality % at Sn, it is difficult controlling to desired softening temperature.In addition, too high in the occasion of Sn because of softening temperature more than 0.009 quality %, in above-mentioned CCL operation, carry out the recrystallization annealing difficulty that becomes, and produce the defective of the reduction and so on of electroconductibility.

Therefore, contain Sn and measure 0.001-0.009 quality %.Preferred 0.002-0.008 quality %, more preferably 0.003-0.007 quality %.

Below, the manufacture method of rolled copper foil is described.

Fig. 9 is the whole schema of manufacturing process of the rolled copper foil of expression embodiments of the present invention.The rolled copper foil of above-mentioned present embodiment is by preparing as raw-material reverberatory refining copper (JISH3100 C1100) or oxygen free copper (JIS H3100 C1020) or containing the copper alloy ingot (ingot casting) of mentioned component (operation is carried out hot rolled hot-rolled process (operation b) a) afterwards; Behind the hot-rolled process, carry out cold rolling cold rolling process (operation c) and elimination process annealing operation (operation d) because of the cold rolling work hardening that causes by suitably implementing repeatedly; Thereby make be called as " blank " through the annealed rolled copper foil.In addition, also will become " blank " process annealing operation before sometimes and be called " blank anneal operation " (operation d ').In " blank anneal operation ", wish to eliminate fully processing strain (for example roughly Full Annealing) before this.

Then, " blank " implemented final cold rolling process (operation e also has the situation that is called as " finish rolling operation "), make the FPC rolled copper foil of specific thickness.In addition, rolled copper foil at this moment is in the state (state that is not annealed) of work hardening.

Rolled copper foil behind the final cold rolling process carries out surface treatment (operation f) as required, supplies with FPC manufacturing process (operation g).Recrystallization annealing as mentioned above, (operation g ') in operation g (for example, CCL operation), carry out often.

In the present invention, so-called " final cold rolling process " is meant operation e, and so-called " recrystallization annealing " operation g ' is meant the operation of carrying out in operation g.

The feature of showing the manufacture method of rolled copper foil of the present invention is, the total reduction of the final cold rolling process before the recrystallization annealing is decided to be more than 94%, and the draught in each road is controlled at 15-50%.Additional features is in this final cold rolling process, control it as " draught in the draught in the draught in first road 〉=second road 〉=the 3rd road ", and each road draught that the 3rd road is later to be controlled at 15-25%.

In addition, so-called total reduction is defined as: total reduction (%)={ 1-(thickness of slab of the thickness of slab/blank behind the final cold rolling process) } * 100.In addition, the draught in so-called each road is meant the decrement when thickness of slab has passed through a pair roller, is defined as: the draught in each road (%)={ 1-(thickness of slab before the thickness of slab after the rolling processing once/this rolling processing) } * 100.

In the final cold rolling process before recrystallization annealing, it is in order to realize rolling surface is had the { 220} of the occupation rate more than 80% that total reduction is decided to be more than 94% _CuPlanar orientation (rolling texture), and be implemented in { the 200} that has the occupation rate more than 90% on the rolling surface by later recrystallization annealing _CuPlanar orientation (cubes texture).In addition, by this recrystallization annealing, be to reach more than the 40 μ m for the median size that makes recrystal grain.

Have again, in the final cold rolling process before recrystallization annealing, each road draught is controlled at 15-50%, especially be controlled to be " draught in the draught in the draught in first road 〉=second road 〉=the 3rd road ", and each road draught that the 3rd road is later is controlled at 15-25% at rolling texture { 111} _CuThe XRD utmost point of face resembles during figure measures, and makes in α=35 { 111} in °-75 ° the scope _CuThe stdn average intensity of face is non-stepped, realizes that perhaps greatly in fact only there is one grain orientation state in the zone.

In final cold rolling process, less than 94% or the control of each road draught do not satisfied the occasion of above-mentioned condition, be not enough for achieving the above object at total reduction.Therefore, total reduction is decided to be more than 94%, and each road draught is controlled at 15-50%.Have again, preferably be controlled to be " draught in the draught in the draught in first road 〉=second road 〉=the 3rd road ", and each road draught that the 3rd road is later is controlled at 15-25%.

Below, the research to draught control is described.

The rolling stress that applies man-hour that adds can consider to be divided into " tensile stress composition " and " stress under compression composition " to processing object.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 (to the orientation orientation of rolling surface) is { 220} in the occasion of stress under compression usually _CuFace is { 311} in the occasion of tensile stress _CuFace or { 211} _CuFace.

In existing rolled copper foil, from above-mentioned viewpoint, the reduction settings in the total reduction of final cold rolling process and each road is got higher, then strengthened { 220} by improving stress under compression _CuPlanar orientation (rolling texture).

In addition, in existing rolled copper foil, only be conceived to the total reduction of final cold rolling process, the draught in each road is then done special consideration.But, improving the occasion of total reduction, from reducing the viewpoint of processing passage, can think that the common practice is that reduction settings with each road gets higher.

Yet, by the inventor studying in great detail of learning of metallic crystal understood, if the reduction settings with each road get higher after, and improve total reduction, in the process of final cold rolling process, produce recrystallize phenomenon etc. partly, hindered { 220} _CuThe formation of planar orientation (rolling texture).In addition, to { 220} _CuMuch less the obstruction that planar orientation (rolling texture) forms, has also hindered three orientations of the cubes texture that is caused by recrystallization annealing.

Therefore, the present invention has illustrated and the draught (stress under compression) in each road has been controlled than after low, and improved the manufacture method of total reduction (accumulation processing strain) with in the past opposite.Therefore, in the recrystallize in being suppressed at final cold rolling process process (the processing strained is eliminated), can form { 220} with the occupation rate more than 80% _CuPlanar orientation (rolling texture).

Other embodiment

In operation a, to fusing, castmethod without limits, and to the size of material also without limits.In operation b, operation c and operation d, also have no particular limits, can be usual method and condition.In addition, the thickness that is used for the rolled copper foil of FPC is generally below the 50 μ m, and the thickness of rolled copper foil of the present invention is as long as below 50 μ m, without limits.

Below, the manufacturing of flexible PCB is described.

Use the rolled copper foil of above-mentioned embodiment, utilize the manufacture method of carrying out usually, can obtain flexible PCB.In addition,, both can heat-treat, and also can adopt other operation to carry out with common CCL operation to the recrystallization annealing of rolled copper foil.

Below, the effect of embodiment is described.

According to above-mentioned embodiments of the present invention, has following effect.

(1) with the rolled copper foil that relatively can obtain having in the past good curved characteristic.

(2) relatively can stably make rolled copper foil with the past with good curved characteristic.

(3) with the flexible distribution of the flexible PCB (FPC) that in the past relatively can obtain having good curved characteristic etc.

(4) not only can be used for flexible PCB (FPC), can also be applicable to other conductive component that requires high curved characteristic (flex life).

Below, further describe the present invention according to embodiment, but the present invention is not subjected to these qualification.

Embodiment

Below, the making of embodiment 1 and comparative example 1-3 is described.

Beginning is made oxygen free copper (oxygen level is 2ppm) as starting material, has made thickness 200mm, the ingot casting of width 650mm.Then, carried out hot rolling after the thickness of 10mm, suitably carried out cold rolling and process annealing repeatedly, made blank with 0.8mm and two kinds of thickness of 0.2mm according to the described flow process of Fig. 9.In addition, as blank anneal, the temperature of having carried out at 700 ℃ is incubated about one minute thermal treatment.

Subsequently, by carrying out final cold rolling process under the conditions shown in Table 1, having made thickness is the rolled copper foil (embodiment 1 and comparative example 1-3) of 16 μ m.In addition, for each condition (each rolled copper foil), each has made five samples.

The condition of the final cold rolling process of table 1

	Sotck thinkness	Final cold rolling process (Copper Foils of blank → thickness 16 μ m)
					Every rolling draught together	Total reduction	Total passage
		Embodiment
1	0.8mm		First road: about 50% the second roads: about 30% 3rd below the road: about 15-25%	About 98%	12
		Comparative example 1				First road: about 60% the second roads: about 40% 3rd below the road: about 30-40%	8
Comparative example 2			0.2mm		First road: about 50% the second roads: about 30% 3rd below the road: about 20-30%			About 92%	8
	Comparative example 3	First road: about 60% the second roads: about 40% 3rd below the road: about 30-40%		5

As shown in table 1, embodiment 1 is the rolled copper foil of embodiments of the present invention.Comparative example 1 is the rolled copper foil that each road draught of final cold rolling process exceeds specialized range of the present invention.Comparative example 2 is rolled copper foils that the total reduction of final cold rolling process exceeds specialized range of the present invention.Comparative example 3 is the total reduction of final cold rolling process and the rolled copper foil that each road draught all exceeds specialized range of the present invention.

Below, the grain orientation state of the rolled copper foil after final cold rolling process is finished is described.

In various XRD determining (utmost point resembles figure and measures for 2 θ/θ mensuration, the mensuration of rocking curve, and orientation is measured in the face), (the リ ガ of Co., Ltd. Network system, model is: RAD-B) to have used the X-ray diffraction device.Anticathode (target) uses Cu, and tube voltage and tube current are respectively 40kV, 30mA.And, be of a size of about 15 * 15mm for the sample of XRD determining ²

The condition that XRD2 θ/θ measures uses general wide-angle protractor to measure in 2 θ=30-100 ° scope.The slit condition that 2 θ/θ measure is 1 ° at divergent slit, and the reception slit is 0.15mm, and scatter slit is to carry out under 1 ° the condition.

In addition, the Shu Erci reflection method that the condition that the XRD utmost point is measured as figure is to use, is a step β angle to be carried out 0-360 ° scanning (rotation) with per 1 ° in α=35 in the scope of °-75 ° (are α=90 ° perpendicular to the direction of rolling surface), has measured { 111} _CuThe diffracted intensity of face (43 ° of 2 θ ≌, 2 θ values have been used the result that each sample has been measured in advance).At this moment slit condition has been used divergent slit=1 °, and scatter slit=7mm receives slit=7mm and Shu Erci slit (slit height 1mm).

To the state that machines of each rolled copper foil (thickness is 16 μ m) made from the condition of table 1 (behind final cold rolling process before the recrystallization annealing), the X-ray diffraction 2 θ/θ that has carried out rolling surface measures and is { the 111} of benchmark with the rolling surface _CuThe utmost point of face resembles figure and measures.Figure 10 is the example of X-ray diffraction 2 θ to the rolling surface/θ measurement result before the recrystallization annealing behind final cold rolling process.Figure 10 (a) is embodiment 1, and Figure 10 (b) is a comparative example 1, and Figure 10 (c) is a comparative example 2, and Figure 10 (d) is a comparative example 3.

In addition, table 2 is illustrated in each measurement result shown in Figure 10, is 100 o'clock relative intensity and { 220} with the diffracted intensity of strong line _CuThe occupation rate of face.

Table 2 is 100 o'clock relative intensity and { 220} with the diffracted intensity of strong line _CuThe face occupation rate

	{111} Cu	{200} Cu	{220} Cu	{311} Cu	{220} CuThe face occupation rate
						Embodiment
1	2	4	100	3	About 92%
						Comparative example 1	2	25	100	5	About 76%
Comparative example 2	6	53	100	6	About 61%
						Comparative example 3	4	100	41	6	About 27%

As indicated in Figure 10 and table 2, embodiment 1 is judged to be to have formed by force and is oriented in { 220} _CuThe rolling texture ({ 220} of face _CuFace occupation rate ≌ 92%).Relative therewith, comparative example 1-3 is judged to be in a large number and detects { 200} _CuFace, { 220} _CuThe face occupation rate also is lower than 80%.

Figure 11 is that the rolling surface with embodiment 1 is the { 111} of benchmark _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 11 (a) expression be β scanning by each α angle obtain should { 111} _CuThe stdn average intensity of the diffraction peak of face, what Figure 11 (b) represented is that positive pole resembles figure.

Figure 12 is that the rolling surface with comparative example 1 is the { 111} of benchmark _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 12 (a) expression be β scanning by each α angle obtain should { 111} _CuThe stdn average intensity of the diffraction peak of face, what Figure 12 (b) represented is that positive pole resembles figure.

Figure 13 is that the rolling surface with comparative example 2 is the { 111} of benchmark _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 13 (a) expression be β scanning by each α angle obtain should { 111} _CuThe stdn average intensity of the diffraction peak of face, what Figure 13 (b) represented is that positive pole resembles figure.

Figure 14 is that the rolling surface with comparative example 3 is the { 111} of benchmark _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 14 (a) expression be β scanning by each α angle obtain should { 111} _CuThe stdn average intensity of the diffraction peak of face, what Figure 14 (b) represented is that positive pole resembles figure.

In Figure 11 (a), Figure 12 (a), Figure 13 (a) and Figure 14 (a), the arrow among the figure represents that the stdn average intensity becomes the part in stepped or very big zone.As indicated in the figure, known in α=35 in °-75 ° the scope that in fact only have a greatly zone for embodiment 1, in contrast, for comparative example 1-3, but there are two places at least in this very big zone.

At this, corresponding with the very big zone of the scope of α=40 of Figure 12 (a) and Figure 14 (a) °-45 °, in Figure 12 (b) and Figure 14 (b), shown in the arrow among the figure, can confirm symmetric diffraction peak four times.These four symmetric diffraction peaks can think to come from the recrystallize phenomenon in the cold rolling course of processing.In addition, comparative example 1 and 3 is all big than the draught of the regulation of the present invention rolled copper foils (with reference to table 1) of draught in each road of final cold rolling process, hints out that the draught in each road has great influence to the recrystallize phenomenon in the cold rolling course of processing.

On the other hand, in Figure 13 (b), do not see corresponding four symmetric diffraction peaks of stepped region with the scope of α=40 of Figure 13 (a) °-45 °.Yet, because comparative example 2 is total reduction rolled copper foils (with reference to table 1) bigger than the total reduction of regulation of the present invention of final cold rolling process, thereby can think, because the rotation phenomenon of the copper crystal of cold rolling processing is insufficient, just detect the stepped region of scope of α=40 °-45 ° of Figure 14 (a).

To show 1-2 and Figure 10-14 merges to get up to consider.If all the draught than regulation of the present invention is big for the draught in each road, then can think, cause the recrystallize phenomenon in the cold rolling course of processing, { 200} in 2 θ/θ measures _CuThe diffraction of face strengthens, and resembles in the figure mensuration at the utmost point and can observe symmetric diffraction peak four times.In addition,, can think then that the rotation phenomenon of the copper crystal that is caused by cold rolling processing becomes insufficient, can observe { 200} in 2 θ/θ measures if total reduction is littler than the total reduction of regulation of the present invention _CuThe diffraction of face strengthens.Therefore, in comparative example 3, because the compound phenomenon of these important factors, can think { the 200} of 2 θ/θ in measuring _CuFace and { 220} _CuThe diffracted intensity of face becomes I{200} _Cu＞I{220} _Cu

With the processing conditions of final cold rolling process and the relation of the grain orientation state of the rolled copper foil after machining be summarized as follows.In the final cold rolling process before recrystallization annealing, very clear, by total reduction is decided to be more than 94%, and each road draught is controlled at 15-50%, especially be controlled to be " draught in the draught in the draught in first road 〉=second road 〉=the 3rd road ", and each road draught that the 3rd road is later is controlled at 15-25%, can control the recrystallize phenomenon in the final cold rolling course of processing, and can form { the 220} of the rotation phenomenon that has promoted copper crystal _CuPlanar orientation (good rolling texture).

On the contrary, " total reduction " and " each road draught " exceeds the scope of the present invention's regulation, then produces recrystallize phenomenon or the rotation of inadequate crystal in the rolling course of processing, will hinder { the 220} of rolled copper foil _CuEffective formation of planar orientation (rolling texture).

Below, the grain orientation state of the rolled copper foil after the recrystallization annealing is described.

To the rolled copper foil of making as mentioned above (thickness is 16 μ m, and final cold rolling process is finished), carrying out using the X-ray diffraction device to estimate the grain orientation state of each rolled copper foil after temperature is 60 minutes recrystallization annealings of 180 ℃ of insulations.{ 220} by XRD2 θ/θ evaluation of measuring cubes texture _Cu(get the mean value of five samples respectively) during the face occupation rate, embodiment 1 is about 94%, and comparative example 1 is about 91%, and comparative example 2 is about 89%, and comparative example 3 is about 88%.It the results are summarized in table 3.

In addition, the mensuration of XRD rocking curve is following carries out.XRD2 θ/θ that detector is fixed on by each rolled copper foil measures the { 200} that obtains _Cu2 θ values of the diffraction peak of face are estimated its full width at half maximum (FWHM) (FWHM to the diffraction peak that obtains when the θ=15-35 ° of scanned sample _{{ 200}}) and integral breadth (IW _{{ 200}}), calculated their ratio IW _{{ 200}}/ FWHM _{{ 200}}In addition, the slit condition of the mensuration of rocking curve and 2 θ/θ measure same, are 1 ° at divergent slit, and the reception slit is 0.15mm, and scatter slit is to carry out under 1 ° the condition.Its result (being respectively the mean value of five samples) is documented in the table 3 together.

In addition, orientation is measured following carrying out in the XRD face.At first, each rolled copper foil (each sample) is tried to achieve { 111} in advance _Cu(for example, use is from { the 111} of JCPDS for 2 θ values of face _Cu2 θ values of face are carried out { 111} _CuOrientation is measured in the face of face, uses the β value of diffracted intensity maximum, by carrying out 2 θ/θ mensuration the sample face being set under the state of α=35 °, just can obtain { the 111} of this sample _Cu2 θ values of face).Detector be fixed on the { 111} of this sample thereafter, _CuAny one of the four subsymmetric diffraction peaks that 2 θ values of face, use have obtained when sample has been carried out β axle scanning (β=0-360 °) estimated its full width at half maximum (FWHM) (FWHM _{{ 111}}) and integral breadth (IW _{{ 111}}), calculated their ratio IW _{{ 111}}/ FWHM _{{ 111}}Its result (being respectively the mean value of five samples) is documented in the table 3 together.

The XRD determining result of the rolled copper foil after the table 3 pair recrystallization annealing (being respectively the mean value of five samples)

	{200} CuThe occupation rate of face	Measuring method	Full width at half maximum (FWHM) FWHM {111}	Integral breadth IW {111}	IW {111}/ FWHM {111}	The stdn average intensity is than [a]/[b]
							Embodiment 1	About 94%	Rocking curve	About 7.8 °	About 8.2 °	About 1.1	About 4.5
Orientation in the face	About 8.3 ° of *	About 8.4 °	About 1.0
				Comparative example 1	About 91%	Rocking curve			About 8.6 °	About 9.4 °	About 1.1	About 2.9
Orientation in the face	About 8.8 ° of *	About 10.4 °	About 1.2
						Comparative example 2	About 89%	Rocking curve	About 7.3 °	About 8.7 °	About 1.2		About 2.0
Orientation in the face	About 9.8 ° of *	About 12.3 °	About 1.3
				Comparative example 3	About 88%			Rocking curve	About 10.4 °	About 12.5 °	About 1.2	About 1.7
Orientation in the face	About 11.8 ° of *	About 14.9 °	About 1.3

Annotate *: full width at half maximum (FWHM) (FWHM during orientation is measured in the face _{{ 111}}) the result be expressed as the average (ave-FWHM of full width at half maximum (FWHM) _{{ 111}}).

The relation of the grain orientation state of the rolled copper foil before and after the recrystallization annealing is summarized as follows.As indicated in the result of table 3, the rolled copper foil that the rolled copper foil that has as the grain orientation state of Figure 11 has been carried out recrystallization annealing is from { 200} _CuThe occupation rate of face, full width at half maximum (FWHM) (FWHM _{{ 111}}), the average (ave-FWHM of full width at half maximum (FWHM) _{{ 111}}), IW _{{ 200}}/ FWHM _{{ 200}}And IW _{{ 111}}/ FWHM _{{ 111}}Demonstrate etc. index and to have three cubes texture that orientation is high.And, than [a]/[b] index, except three orientations of cubes texture, also show it is { 200} according to the stdn average intensity _CuThe twin crystal of face is organized few rolled copper foil.

In contrast, the rolled copper foil that the rolled copper foil that has as the grain orientation state of Figure 12-14 has been carried out recrystallization annealing, all very poor more than any one of above-mentioned a plurality of indexs, demonstrate three orientations very poor (obstruction) of cubes texture, and/or to demonstrate be { the 200} of cubes texture _CuThe rolled copper foil that the twin crystal tissue of face is many.

Below, the average crystal grain particle diameter of the rolled copper foil after the recrystallization annealing is described.

Following the carrying out of evaluation to the average crystal grain particle diameter of each rolled copper foil (thickness is 16 μ m, after the recrystallization annealing) of making as mentioned above.In order to aquae hydrogenii dioxidi (for example, Wako Pure Chemical Industries, Ltd.'s system, the trade mark: 080-01186) and ammoniacal liquor (for example, Wako Pure Chemical Industries, Ltd.'s system, the trade mark: the surface of the wetting absorbent cotton of mixing solutions 017-03176) (ammoniacal liquor 10ml+ aquae hydrogenii dioxidi 2-3 drips) corrosion rolled copper foil (with the degree of corrosive face) with absorbent cotton wiping 1-2 time afterwards, use opticmicroscope (オ リ Application パ ス Co., Ltd. system, model: PMG3) taken surperficial metal structure photo.This photo is tried to achieve the average crystal grain particle diameter according to the process of chopping of JIS H 0501.It the results are shown in table 4.

The measurement result of the average crystal grain particle diameter of the rolled copper foil after table 4 recrystallization annealing (oxygen free copper) (being respectively the mean value of five samples)

	The average crystal grain particle diameter
		Embodiment
1	About 71 μ m
		Comparative example 1	About 34 μ m
Comparative example 2	About 8.5 μ m
		Comparative example 3	About 6.9 μ m

As indicated in the result of table 4, the rolled copper foil of embodiment 1 and comparative example 1-3 relatively have very large average crystal grain particle diameter as can be known.This result can think to come from high three orientations and the { 200} of the cubes texture of embodiment 1 _CuThe twin crystal of face is organized few rolled copper foil (with reference to table 3).

Below, the curved characteristic of the rolled copper foil after the recrystallization annealing is described.

Following the carrying out of evaluation to the curved characteristic of each rolled copper foil (thickness is 16 μ m, after the recrystallization annealing) of making as mentioned above.Figure 17 is the synoptic diagram of the summary of expression curved characteristic evaluation (slip pliability test).The slip bend test device uses the エ of SHIN-ETSU HANTOTAI Application ジ ニ ア リ Application グ Co., Ltd. system, model: SEK-31B2S; The condition of measuring is: R=2.5mm, and amplitude size=10mm, frequency=25Hz (amplitude speed=1500 time/minute), specimen width=12.5mm, specimen length=220mm, the length direction of coupons are rolling direction.It the results are shown in table 5.

The slip pliability test result (being respectively the mean value of five samples) of the rolled copper foil after table 5 recrystallization annealing (oxygen free copper)

	The flex life number of times is up to the number of times of bend fracture
		Embodiment
1	6.6×10 6
		Comparative example 1	3.2×10 6
Comparative example 2	1.0×10 6
		Comparative example 3	0.9×10 6

As indicated in the result of table 5, the rolled copper foil of embodiment 1 and comparative example 1-3 relatively have the above flex life number of times (high curved characteristic) of twice as can be known.This result can think to come from high three orientations and the { 200} of the cubes texture of embodiment 1 _CuThe twin crystal of face is organized few rolled copper foil (with reference to table 3) and big average crystal grain particle diameter (with reference to table 4).

Below, the making of embodiment 2-3 and comparative example 4 is described.Made as starting material: the copper alloy (embodiment 2) that in above-mentioned oxygen free copper (oxygen level is 2ppm), has added 0.004 quality %Sn, in above-mentioned oxygen free copper, add the copper alloy (embodiment 3) of 0.007 quality %Sn and in above-mentioned oxygen free copper, added the copper alloy (comparative example 4) of 0.01 quality %Sn, having made thickness is 200mm, and width is the ingot casting of 650mm.Then, carry out hot rolling after the thickness of 10mm, suitably carry out cold rolling repeatedly and the process annealing operation, make blank with 0.8mm thickness according to the described flow process of Fig. 9.In addition, carried out the about 1 minute thermal treatment of insulation under 700 ℃ of temperature as blank anneal.

Subsequently, by carry out final cold rolling process under the condition (with reference to table 1) identical with embodiment 1, having made thickness is the rolled copper foil (embodiment 2-3 and comparative example 4) of 16 μ m.These rolled copper foils (final cold rolling machining) have been carried out that X-ray diffraction 2 θ/θ measures and have been { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles figure when measuring, and can obtain and Figure 10 (a) and the same result of Figure 11.

Softening temperature to the rolled copper foil (embodiment 2-3 and comparative example 4) made is studied.Research method is the stretching test method of cardinal principle according to JIS Z 2241, and (Shimadzu Scisakusho Ltd's system, model: tensile strength AG-1) is judged to have used universal testing machine.At first, being cut into width as coupons is 15mm, and length is the rectangle (length direction is a rolling direction) of 200mm.Each coupons that is cut into carried out 30 minutes thermal treatment each temperature of 50 ℃, 100 ℃, 130 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃.The tensile strength of each coupons after the mensuration thermal treatment reduces the (110-150N/mm that reaches capacity basically with intensity ²Degree) (in addition, the tensile strength of the rolled copper foil before the thermal treatment is 380-480N/mm to temperature as softening temperature ²Degree).

Carried out result's (being respectively the mean value of five samples) of such research, the softening temperature of embodiment 2 is about 180 ℃, and the softening temperature of embodiment 3 is about 260 ℃, and the softening temperature of comparative example 4 is about 320 ℃.In addition, the softening temperature that does not contain the oxygen free copper (embodiment 1) of Sn is about 100 ℃.For these rolled copper foils, after having carried out thermal treatment under the condition of being scheduled to recrystallization annealing in the CCL operation (being incubated 10 minutes down for 300 ℃), estimate and curved characteristic evaluation (slip pliability test) with the above-mentioned average crystal grain particle diameter that similarly carried out in temperature.The evaluation of average crystal grain particle diameter the results are shown in table 6, the curved characteristic evaluation the results are shown in table 7.

The average crystal grain particle size determination result (being respectively the mean value of five samples) of the rolled copper foil after table 6 thermal treatment (copper alloy)

	The average crystal grain particle diameter
		Embodiment
2	About 65 μ m
		Embodiment 3	About 60 μ m
Comparative example 4	About 11 μ m

The slip pliability test result (being respectively the mean value of five samples) of the rolled copper foil after table 7 thermal treatment (copper alloy)

	The flex life number of times is up to the number of times of bend fracture
		Embodiment
2	6.7×10 6
		Embodiment 3	6.1×10 6
Comparative example 4	0.2×10 6

If take all factors into consideration the result of table 4-7, can think, because embodiment 2 and 3 rolled copper foil have carried out necessary and sufficient recrystallization annealing, thus with existing rolled copper foil (comparative example 1-3) relatively, demonstrate the above flex life number of times (high curved characteristic) of twice.In addition,, can think that the average crystal grain particle diameter after the thermal treatment has enough sizes (more than the 40 μ m) according to same reason.

In addition, for the rolled copper foil that has carried out above-mentioned heat treated embodiment 2 and 3, carrying out XRD 2 θ/θ mensuration, { 200} similarly to Example 1 _CuThe rocking curve of face is measured and is { the 111} of benchmark with the rolling surface _CuWhen the XRD utmost point of face resembles figure mensuration (orientation is measured in the face, the evaluation of stdn average intensity ratio), can confirm { the 200} more than 90% respectively _CuThe occupation rate of face, FWHM _{{ 200}}≤ 10 °, 0.85≤IW _{{ 200}}/ FWHM _{{ 200}}≤ 1.15, ave-FWHM _{{ 111}}≤ 10 °, 0.85≤IW _{{ 111}}/ FWHM _{{ 111}}≤ 1.15 and [a]/[b] 〉=3.

On the other hand, the comparative example 4 that the content of Sn composition is Duoed than the scope of the present invention's regulation, its curved characteristic is poorer than existing rolled copper foil (comparative example 1-3).Therefore, carry out the XRD utmost point for the rolled copper foil that has carried out above-mentioned heat treated comparative example 4 and resembled figure mensuration.Figure 18 be comparative example 4 be { the 111} of benchmark with the rolling surface _CuThe XRD utmost point of face resembles an example of figure measurement result.Figure 18 (a) expression be { the 111} that the β scanning by each α angle obtains _CuThe stdn average intensity of the diffraction peak of face, what Figure 18 (b) represented is that positive pole resembles figure.

As indicated in the result among the figure, the stdn average intensity is than being [a]/[b]≤3, and the diffraction that comes from the diffraction of recrystallize as can be known and come from rolling texture mixes and exists.This can think because the content of Sn composition is too much, thereby recrystallization annealing can not be carried out fully.

Claims (11)

1. rolled copper foil, carrying out it is characterized in that in the rolled copper foil of recrystallization annealing behind final cold rolling process:

Resemble figure according to the X-ray diffraction utmost point that with the rolling surface is benchmark and measure the result obtain, the above-mentioned { 111} that scans at the β that establishes that the above-mentioned X-ray diffraction utmost point resembles that figure measures by α=35 ° and α=74 ° _CuWhen the stdn average intensity of the diffraction peak of face is respectively [a] and [b], have [a]/the grain orientation state of [b] 〉=3.

2. rolled copper foil according to claim 1 is characterized in that:

According to measuring the result who obtains, { 111} by orientation in the X-ray diffraction face _CuFace is with respect to { the 200} of the rolling face _CuAverage (the ave-FWHM of the full width at half maximum (FWHM) of the diffraction peak of face _{{ 111}}) be below 10 °.

3. rolled copper foil according to claim 1 is characterized in that:

According to X-ray diffraction 2 θ of the rolling face/θ is measured the result who obtains, the diffraction peak of copper crystal be above-mentioned { 200} more than 90% _CuFace, and,

According to above-mentioned { 200} _CuThe X-ray diffraction rocking curve of face is measured the result who obtains, the full width at half maximum (FWHM) (FWHM of this diffraction peak _{{ 200}}) be below 10 °.

4. rolled copper foil according to claim 1 is characterized in that:

According to X-ray diffraction 2 θ of the rolling face/θ is measured the result who obtains, the diffraction peak of copper crystal be above-mentioned { 200} more than 90% _CuFace, and,

According to above-mentioned { 200} _CuThe X-ray diffraction rocking curve of face is measured the result who obtains, the full width at half maximum (FWHM) (FWHM of this diffraction peak _{{ 200}}) and integral breadth (IW _{{ 200}}) ratio be 0.85≤IW _{{ 200}}/ FWHM _{{ 200}}≤ 1.15, and,

Measure the result who obtains according to resembled figure by the X-ray diffraction utmost point that with above-mentioned rolling surface is benchmark, the grain orientation state that has is: at above-mentioned { 111} _CuFace is with respect to above-mentioned { 200} _CuIn 4 asymmetrical diffraction peak values of face, the full width at half maximum (FWHM) (FWHM of any one diffraction peak _{{ 111}}) and integral breadth (IW _{{ 111}}) ratio be 0.85≤IW _{{ 111}}/ FWHM _{{ 111}}≤ 1.15.

5. rolled copper foil according to claim 1 is characterized in that:

Median size at viewed this recrystal grain on the rolling face is more than the 40 μ m.

6. rolled copper foil according to claim 1 is characterized in that:

Comprise the Sn of 0.001-0.009 quality % in the copper alloy as the rolled copper foil use, all the other are Cu and unavoidable impurities.

7. rolled copper foil in the rolled copper foil behind final cold rolling process before the recrystallization annealing, is characterized in that:

Measure the result who obtains according to resemble figure by the X-ray diffraction utmost point that with the rolling surface is benchmark, at { the 111} that will obtain by the β scanning of each α angle _CuWhen the stdn average intensity of the diffraction peak of face plotted curve, the grain orientation state that has was: above-mentioned α angle is that the above-mentioned stdn average intensity of 35 ° of-75 ° of scopes is non-stepped, perhaps, in fact only has a greatly zone.

8. rolled copper foil according to claim 7 is characterized in that:

According to X-ray diffraction 2 θ of rolling surface/θ is measured the result who obtains, the diffraction peak of copper crystal be { 220} more than 80% _CuFace.

9. rolled copper foil according to claim 7 is characterized in that:

Comprise the Sn of 0.001-0.009 quality % in the copper alloy as the rolled copper foil use, all the other are Cu and unavoidable impurities.

10. the manufacture method of a rolled copper foil, in the rolled copper foil behind final cold rolling process before the recrystallization annealing, the Copper Foil of manufacturing resembles figure according to the X-ray diffraction utmost point that with the rolling surface is benchmark and measures the result who obtains, at { the 111} that will be obtained by the β scanning of each α angle _CuWhen the stdn average intensity of the diffraction peak of face plotted curve, above-mentioned α angle was that the above-mentioned stdn average intensity of 35 ° of-75 ° of scopes is non-stepped, perhaps, in fact only had a greatly zone; It is characterized in that:

The total reduction of the final cold rolling process before the recrystallization annealing is decided to be more than 94%, and the draught in each road is controlled at 15-50%.

11. the manufacture method of rolled copper foil according to claim 10 is characterized in that:

In the final cold rolling process before recrystallization annealing, control the draught that the rolling draught in each road makes draught 〉=the 3rd road in draught 〉=second road of winning, and the later draught in per three roads is controlled at 15-25%.

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