CN103540787A

CN103540787A - Rolled copper foil

Info

Publication number: CN103540787A
Application number: CN201310050643.2A
Authority: CN
Inventors: 室贺岳海; 关聪至
Original assignee: SH Copper Products Co Ltd
Current assignee: SH Copper Products Co Ltd
Priority date: 2012-07-17
Filing date: 2013-02-08
Publication date: 2014-01-29
Also published as: JP2014019892A; KR102002346B1; KR20140010867A; JP5373940B1

Abstract

The invention provides a rolled copper foil which has high bending characteristics and excellent bending resistance. A plurality of crystal surfaces parallel to a main surface comprises a (022) face, a (002) face, a (113) face, a (111) face and a (133) face. The diffraction peak intensities of the crystal faces calculated by performing X-ray diffraction measurement with 2 theta/theta method on the main surface and setting the summing value as 100 is I (022)+i(002)>=75.0Measured using X-ray pole figure of (111) method diffraction peak intensity of the average plane of plotting the graph obtained, the inclination angle of the (111) plane intensity of the diffraction peak of the average straight line connecting each DEG and 53 DEG when the ordinate intercept of the (A) and the inclination angle of the (111) plane of the maximum average intensity of a diffraction peak within the range of 90 DEG or less than 15 DEG (B) f (A) / (B) >= 1/4, and surface roughness of the main surface, the ten point average roughness Rzjis <=1.2(mu)m, the arithmetic mean roughness Ra <=0.3(mu)m.

Description

Rolled copper foil

Technical field

The present invention relates to a kind of rolled copper foil, and be particularly related to a kind of rolled copper foil that can be used for flexibility printed circuit board.

Background technology

Flexibility printed circuit board (FPC:Flexible Printed Circuit), due to thin thickness, flexible excellence is therefore high to the degree of freedom of the mounting means of electronics etc.Therefore, FPC mostly can be for the bending part of Collapsible mobile telephone, digital camera, the first-class moving part of printer, and the distribution of the moving part of the CD relevant device such as hard disk drive (HDD:Hard Disk Drive), digital versatile disc (DVD:Digital Versatile Disk), compact disk (CD:Compact Disk) etc.Therefore, the rolled copper foil for as FPC, its wiring material requires high curved characteristic always, bears the excellent resistance to bend(ing) of alternating bending.

Rolled copper foil that FPC uses is manufactured through hot rolling, the operation such as cold rolling.Rolled copper foil, after FPC manufacturing process in, by caking agent or directly wait and fitted by the formed FPC basement membrane of the resins such as polyimide (base material) by heating.Rolled copper foil on base material forms distribution by implementing the surface working such as etching.By the hard state after cold rolling after the state after the softening annealing of recrystallization and rolling sclerosis, compare, the resistance to bend(ing) of rolled copper foil significantly improves.Therefore, in the manufacturing process of for example above-mentioned FPC, use the rolled copper foil after cold rolling, avoid the distortion such as elongation, fold, and meanwhile cutting rolled copper foil, and overlapped on base material.Then, hold concurrently and to heat with the full annealed of rolled copper foil, make thus rolled copper foil and base material closely sealed and carry out integrated.

Take above-mentioned FPC manufacturing process is prerequisite, the rolled copper foil of resistance to bend(ing) excellence and manufacture method thereof have been carried out to various research up to now, and a lot of reports are pointed out: on the surface of rolled copper foil, as cubes orientation { 002} face ({ 200} face) reaches all the more, and resistance to bend(ing) more improves.

For example, in patent documentation 1, under being the condition of 5 μ m～20 μ m, the median size of recrystallization grain carries out final annealing before cold rolling.In addition it is more than 90%, making final rolling degree of finish when cold rolling.Thus, obtain carrying out under modified state in order to form recrystallization tissue, take that rolling surface obtained by X-ray diffraction the intensity of 200} face as I, the micropowder copper of take by X-ray diffraction, obtained { intensity of 200} face is I ₀time, I/I ₀the cubes texture of >20.

In addition, for example, in patent documentation 2, it is more than 93% improving the flourishing degree of final cubes texture before cold rolling and making final degree of finish when cold rolling.Again by implementing full annealed, thereby obtain that { integrated intensity of 200} face is I/I ₀rolled copper foil>=40, that cubes texture is significantly flourishing.

In addition, for example, in patent documentation 3, the total degree of finish while making final cold rolling process is more than 94%, and the degree of finish of every 1 passage (pass) is controlled to 15%～50%.Thus, after full annealed, can obtain the grain orientation state of regulation.That is to say, in the rolling surface by X-ray diffraction pole graph mensuration gained, { 111} face is with respect to { in the face of 200} face, orientation degree Δ β is below 10 °.In addition, in rolling surface as cubes texture the diffraction peak intensity [a] after the stdn of 200} face with { ratio of the diffraction peak intensity [b] after the crystal region stdn in twin relation in 200} face is [a]/[b] >=3.

As mentioned above, in the prior art, by improving total degree of finish of final cold rolling process, after full annealed operation, make the cubes texture of rolled copper foil flourishing, thereby realized the raising of resistance to bend(ing).

Prior art document

Patent documentation

Patent documentation 1: No. 3009383 communique of Japanese Patent

Patent documentation 2: No. 3856616 communique of Japanese Patent

Patent documentation 3: No. 4285526 communique of Japanese Patent

Summary of the invention

The problem that invention will solve

On the other hand, in recent years, along with miniaturization, the slimming of electronics, the situation that FPC is bent and is encased in little space increases gradually.Particularly at the faceplate part of smart mobile phone etc., also sometimes the FPC that is formed with distribution is bent into 180 ° and pack into.Therefore,, for rolled copper foil, allow to improve constantly compared with the requirement of the resistance to bending of small-bend radius.

As mentioned above, according to the difference of purposes etc., may produce and bear the resistance to bend(ing) of alternating bending and bear the different requirements compared with the resistance to bending of small-bend radius.In order to tackle these different requirements, according to various uses, manufacture respectively the rolled copper foil of different qualities in the past.Yet, there is the poor problem of rentability in this situation efficiency that is far from being from productivity aspect.

The object of the present invention is to provide a kind ofly after full annealed operation, can possess the rolled copper foil of high resistance to bend(ing) and excellent resistance to bending simultaneously.If can realize this rolled copper foil with two specific characters, any purposes in the purposes that can be applicable to pay attention to the purposes of resistance to bend(ing) and pay attention to resistance to bending.Therefore, no matter be in the manufacture of rolled copper foil, or in the manufacture of FPC, can enhance productivity significantly.

The method of dealing with problems

According to the 1st mode of the present invention, a kind of rolled copper foil is provided, it is to possess major surfaces, and has the rolled copper foil after final cold rolling process, before full annealed operation with a plurality of crystal faces of described major surfaces in parallel, wherein

Aforementioned a plurality of crystal face comprise 022} face, 002} face, 113} face, 111} face and 133} face,

To use 2 θ/θ method to carry out diffraction peak intensity that X-ray diffraction mensuration is obtained, that the aggregate value of take is 100 aforementioned each crystal faces that convert than being made as respectively I to aforesaid major surfaces?<022}, I?<002}, I?<113}, I?<111}and I?<133}time, I?<022}+ I?<002}>=75.0,

Use X ray utmost point figure method, for a plurality of angles of inclination in 15 ° of above 90 ° of following scopes, obtain respectively make the face internal rotation angle degree of aforesaid major surfaces in the more than 0 ° scope below 360 °, change measured the diffraction peak average intensity of 111} face,

The former angle of inclination of stating is transverse axis, take diffraction peak intensity as the longitudinal axis, to aforementioned { when the diffraction peak average intensity of 111} face is drawn and makes graphic representation, at aforementioned when connecting aforementioned angle of inclination and be 47 °, { { vertical axis intercept of the straight line of the diffraction peak average intensity of 111} face is made as [A] for aforementioned when the diffraction peak average intensity of 111} face and aforementioned angle of inclination are 53 °, aforementioned { when the maximum value of the diffraction peak average intensity of 111} face is made as [B] by aforementioned angle of inclination in more than 15 ° 90 ° of following scopes, [A]/[B] >=1/4

And the surfaceness of aforesaid major surfaces is, 10 mean roughness Rzjis≤1.2 μ m, arithmetic average roughness Ra≤0.3 μ m.

According to the 2nd mode of the present invention, a kind of rolled copper foil as described in the 1st mode is provided, it take oxygen free copper or tough pitch copper is principal constituent.

According to the 3rd mode of the present invention, a kind of rolled copper foil as described in the 1st or the 2nd mode is provided, its added in silver, boron, titanium, tin at least any.

According to the 4th mode of the present invention, a kind of rolled copper foil as described in any one in the 1st～3rd mode is provided, its thickness is below 20 μ m.

According to the 5th mode of the present invention, a kind of rolled copper foil as described in any one in the 1st～4th mode is provided, it is for flexibility printed circuit board.

Invention effect

According to the present invention, provide a kind of after full annealed operation, can possess the rolled copper foil of the resistance to bending of high resistance to bend(ing) and excellence simultaneously.

Accompanying drawing explanation

Fig. 1 means the schema of manufacturing process of the rolled copper foil of one embodiment of the present invention.

Fig. 2 means the figure of the X-ray diffraction measuring method summary in embodiments of the invention and comparative example.

Fig. 3 is the measurement result of using the X-ray diffraction of 2 θ/θ method, wherein (a) is the X-ray diffractogram of the rolled copper foil of the embodiment of the present invention 1, (b) being the X-ray diffractogram of the rolled copper foil of embodiment 2, is (c) X-ray diffractogram of the rolled copper foil of comparative example 3.

Fig. 4 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing the embodiment of the present invention 1.

Fig. 5 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing the embodiment of the present invention 2.

Fig. 6 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing the embodiment of the present invention 3.

Fig. 7 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing the embodiment of the present invention 4.

Fig. 8 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 1.

Fig. 9 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 2.

Figure 10 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 3.

Figure 11 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 4.

Figure 12 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 5.

Figure 13 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 6.

Figure 14 is the { graphic representation of the diffraction peak average intensity made of 111} face of drawing comparative example 7.

Figure 15 is the mode chart of slip bend test device of measuring the resistance to bend(ing) of the rolled copper foil in the embodiment of the present invention.

Figure 16 means the figure of the resistance to bending test method summary of the rolled copper foil in the embodiment of the present invention.

Figure 17 is the antipole point diagram of fine copper shaped metal, and wherein (a) means the antipole point diagram of the crystallization sense of rotation producing by tensile deformation, (b) means the antipole point diagram of the crystallization sense of rotation producing by compression set.

Figure 18 is in general antipole point diagram, depict 013} face, 023} face and with the figure in the less crystal face region of the azimuth difference of these crystal faces.

Nomenclature

10 slip bend test devices

11 sample retaining plates

12 screws

13 vibration transfer part

14 vibration driving bodies

20 partitions

50 coupons

Embodiment

The opinion > of the gained such as the < inventor

As mentioned above, in order to obtain the rolled copper foil of desired excellent resistance to bend(ing) in FPC purposes, the cubes orientation of rolling surface is reached all the more better.The inventor etc. have also carried out various experiments in order to increase the occupation rate in cubes orientation.And by current experimental result, confirmed, existing after final cold rolling process 022} face by after full annealed operation and by modified while being recrystallization, formation { 002} face, is cubes orientation.That is to say, preferably, after final cold rolling process, before full annealed operation, { 022} face is main orientation.

On the other hand, even if the content and the inventor that record as above-mentioned patent documentation 1～3 wait as shown in the trial of carrying out, demonstrate a lot of cubes texture, in obtaining the rolled copper foil that polycrystalline constructs, as cubes texture { 002} face can not account for 100% yet.This is also the same before full annealed operation, under the state before full annealed operation as main orientation 022} face, keep before and after the recrystallization crystal orientation { 002} face, a plurality of { 113} face, { 111} face, { 133} face, { 013} face, { crystal face in the secondary orientation such as 023} face is not controlled and is mixed existence.And the crystal grain with these a plurality of crystal faces is considered to produce various impacts to the various characteristics of rolled copper foil.Therefore, the crystal face in the secondary orientation that the inventor etc. are conceived to think so far useless, constantly can research not reduce the occupation rate in main orientation and maintain high resistance to bend(ing), also by the crystal face in these secondary orientation, improves other characteristic of rolled copper foil simultaneously, for example, require in recent years the resistance to bending of raising.

In this research, { 113} face, { 111} face, { 133} face, { 013} face, { analyze to comprising by the diffraction peak of the rolled copper foil major surfaces of the crystal face in the secondary orientation such as 023} face for the inventor etc.Diffraction peak shows the existence in each secondary orientation, and by its strength ratio, can be learnt the occupation rate in each secondary orientation.The result of this active research is, the discoveries such as the inventor are by carrying out various regulations and they being controlled to the state of this diffraction peak, even by control main orientation { 022} face and having obtained under the situation of high resistance to bend(ing) also can further improve resistance to bending.

In addition, meanwhile, the inventor etc., in order to obtain the high rolled copper foil of desired resistance to bending in FPC purposes, have further carried out active research.Found that, the concavo-convex state of not only crystal orientation, and rolled copper foil major surfaces also has a great impact for resistance to bending.

The present invention's these opinions based on discoveries such as contrivers complete.

< one embodiment of the present invention >

(1) formation of rolled copper foil

First, the formation of crystalline structure of the rolled copper foil of one embodiment of the present invention etc. is described.

(summary of rolled copper foil)

The rolled copper foil of present embodiment, for example, be configured to and possess tabular as the rolling surface of major surfaces.This rolled copper foil is to implementing the rolled copper foil after final cold rolling process, before full annealed operation that hot-rolled process described later, cold rolling process etc. form specific thickness such as take the fine copper such as oxygen free copper (OFC:Oxygen-Free Copper), tough pitch copper as raw-material ingot bar.

The rolled copper foil of present embodiment, for can be for the flexible wiring material applications of for example FPC, by total degree of finish be more than 90%, more preferably more than 94% final cold rolling process to be configured to thickness be below 20 μ m.Then, this rolled copper foil as mentioned above, for example, is held concurrently and is implemented full annealed operation with the bonding process with FPC base material, and attempt to possess excellent resistance to bend(ing) by recrystallization.

As raw-material oxygen free copper, be for example JIS C1020, the purity of the defineds such as H3100 is more than 99.96% copper product.Oxygen level can be not exclusively zero, for example, can contain the oxygen of several ppm left and right.In addition, tough pitch copper is for example JIS C1100, and the purity of the defineds such as H3100 is more than 99.9% copper product.The in the situation that of tough pitch copper, oxygen level is for example 100ppm～600ppm left and right.Sometimes also in these copper products, add the interpolation material of the regulations such as micro-silver (Ag) and form lower concentration copper alloy, thereby form the rolled copper foil that has regulated the various characteristicses such as thermotolerance.In the rolled copper foil of present embodiment, can comprise fine copper and lower concentration copper alloy these two, and raw-material copper material, add material and exert an influence hardly for the effect of present embodiment.

The thickness of the workpiece before final cold rolling process (copper coin material) is being made as to T _b, the processing object after final cold rolling process thickness be made as T _atime, total degree of finish of final cold rolling process is by total degree of finish (%)=[(T _b-T _a)/T _b] * 100 represent.By making total degree of finish be more than 90%, more preferably more than 94%, can obtaining the rolled copper foil of resistance to bend(ing) excellence.

(crystalline structure of rolling surface)

In addition, the rolled copper foil of present embodiment has a plurality of crystal faces parallel with rolling surface.Specifically, under the state after final cold rolling process, before full annealed operation, a plurality of crystal faces comprise { 022} face, { 002} face, { 113} face, { 111} face and { 133} face.{ 022} face becomes the main orientation of rolling surface, and other each crystal face is secondary orientation.

As mentioned above, the state of this each crystal face is controlled by the scale relation of the state of the diffraction peak intensity of having stipulated each crystal face to measure etc.The diffraction peak intensity of each crystal face can be by using 2 θ/θ method the rolling surface of rolled copper foil is carried out to X-ray diffraction mensuration and obtain.Herein, the summary of measuring for the X-ray diffraction that uses 2 θ/θ method, Fig. 2 of reference embodiment described later and comparative example describes.In addition, the details of measuring for X-ray diffraction, describes below.

As shown in Figure 2, the coupons 50 of rolled copper foil etc. being configured to can be around θ axle, ψ axle, these 3 scan axises rotation of φ axle.In the X-ray diffraction that uses 2 θ/θ method is measured, make coupons 50 around the rotation of θ axle, and with angle θ, inject incident X-rays with respect to coupons 50.And, detect the diffraction X ray with angle 2 θ diffraction with respect to the incident direction of incident X-rays.Thus, coupons 50 can be obtained by the intensity of the occupation rate on major surfaces corresponding to each crystal face with the diffraction peak of each crystal face major surfaces in parallel.

It is 100 ratio that the diffraction peak intensity of above-mentioned 5 crystal faces of measuring by this X-ray diffraction is converted into aggregate value, and what obtain is that the diffraction peak intensity of each crystal face compares I?<022}, I?<002}, I?<113}, I?<111}and I?<133}.This diffraction peak intensity is than probably equaling the occupation rate of each crystal face in rolling surface.

By the diffraction peak intensity of each crystal face obtain as representative { conversion formula (A) of the diffraction peak intensity ratio of 022} face is as follows.The diffraction peak intensity of each crystal face is made as respectively to I ' herein,?<022}, I '?<002}, I '?<113}, I '?<111}and I '?<133}.

[several 1]

In the rolled copper foil of present embodiment, { 022} face and the { relation that the diffraction peak intensity ratio of 002} face is set up for following formula (1).

I _{022}+I _{002}≥75.0…（1）

In addition, the rolled copper foil of regulation present embodiment, except above-mentioned formula (1), also meets the numerical value that uses X ray utmost point figure (pole graph) to obtain.Herein, the summary for using X ray utmost point figure (Pole-Figure) method to measure, describes with reference to Fig. 2.In addition, for the detailed content of this mensuration, describe hereinafter.

As shown in Figure 2, in the mensuration of reflection method of using X ray utmost point figure method, further make said sample sheet 50 around the rotation of ψ axle, and and 2 θ/θ method similarly to the detection of diffracted X ray respectively of a plurality of angle of inclination ψ in 15 ° of above 90 ° of following scopes.At this moment, in the ψ of each angle of inclination, maintain this angle on one side, Yi Bian make said sample sheet 50 around the rotation of φ axle, face internal rotation angle degree φ more than 0 ° is being changed in the scope below 360 °, measure, and obtain respectively { the diffraction peak average intensity of 111} face of the copper crystal of gained.

Below explanation uses each average intensity of being obtained by this mensuration to carry out the method for the rolled copper foil in regulation present embodiment.

Take angle of inclination ψ as transverse axis, take diffraction peak intensity as the longitudinal axis, draw that above-mentioned { average intensity of the diffraction peak of 111} face, production example is the such graphic representation of Fig. 4 of embodiment 1 as described later.

For example, as shown in Figure 4, { { the diffraction peak average intensity of 111} face when the diffraction peak average intensity of 111} face and angle of inclination ψ are 53 ° while being 47 ° with straight line connection angle of inclination ψ.Thus, obtain the vertical axis intercept of this straight line.At this moment, this vertical axis intercept is made as to [A].

In addition, by within the scope of graphic representation, be angle of inclination ψ be in 15 ° of above 90 ° of following scopes { maximum value of the diffraction peak average intensity of 111} face is made as [B].At this moment, in the rolled copper foil of present embodiment, meet with following formula (2).

[A]/[B]≥1/4…（2）

Above, by meeting the condition by formula (1), (2) defined, the rolled copper foil of present embodiment can be configured to: after full annealed operation, have the high resistance to bend(ing) of the alternating bending of bearing and bear the excellent resistance to bending compared with small-bend radius.

(surfaceness of rolling surface)

The rolled copper foil of present embodiment, except above-mentioned formation, also further has following surfaceness.

In the rolled copper foil of present embodiment, the surfaceness of rolling surface, in 10 mean roughness Rzjis and arithmetic average roughness Ra, is stipulated shown in (3), (4).

10 mean roughness Rzjis≤1.2 μ m ... (3)

Arithmetic average roughness Ra≤0.3 μ m ... (4)

In addition, 10 mean roughness described herein and arithmetic average roughness, be 10 mean roughness Rzjis and the arithmetic average roughness Ra by JIS B0601:2001 separate provision.The expression mark of the surfaceness being defined respectively by JIS standard had change, a little easily produced and obscured.For the purpose of prudent, in following table 1, represent the change about the JIS standard of surfaceness.

[table 1]

10 mean roughness Rzjis and arithmetic average roughness Ra are obtained by the roughness curve of measuring gained by roughness.

That is to say, for 10 mean roughness Rzjis, first from roughness curve, only in its average line direction, select datum length.The average line of selecting part by this is measured summit and the lowest point of specified quantity in vertical multiplying power direction.At this moment, obtain the mean value sum of the mean value of summit absolute altitude absolute value and the lowest point absolute altitude absolute value of minimum 5 paddy in the lowest point to the at 5 peaks of the highest summit to the.The mean value sum that represents them with micron (μ m), is 10 mean roughness Rzjis.

In addition, for arithmetic average roughness Ra, add up to the average line of selecting from roughness curve to the absolute value of measuring the deviation of curve, obtain mean value.That is to say, with micron (μ m), represent the above-mentioned mean value of obtaining divided by length L by roughness curve and the resulting area of average line, be arithmetic average roughness Ra.

According to foregoing, the rolled copper foil of present embodiment is configured to: after full annealed operation, have high resistance to bend(ing) and excellent resistance to bending simultaneously.

(2) give the characteristic of rolled copper foil

For the characteristic of giving rolled copper foil by possessing above-mentioned crystalline structure, surfaceness, explanation as follows.

(about the crystalline structure of formula (1) defined)

As mentioned above, before full annealed operation { 022} face is changed to after full annealed operation that { 002} face { under 002} face is also directly remaining after full annealed operation, improves the resistance to bend(ing) of rolled copper foil before full annealed operation thus.In addition, when full annealed operation, although { crystal orientation of 002} face itself can not change, and it forms kind of a crystalline substance, thereby promotes that { 022} is towards { 002} face changes growth.Therefore,, by meet above-mentioned formula (1) before full annealed operation, can fully obtain this effect.

But,, can there is not { 002} face herein yet.That is to say, { diffraction peak intensity of 002} face compares I?<002}can be zero.Hence one can see that, in above-mentioned formula (1), for example, at I?<022}+ I?<002}=80.0+0=80.0 and I?<022}+ I?<002}during=60.0+20.0=80.0, after full annealed operation, can be possessed { the same rolled copper foil roughly each other of 002} face crystal structure.In addition, more high better by the numerical value of above-mentioned formula (1) defined, up to now, also do not confirm higher limit.

(about the crystalline structure of formula (2) defined)

In addition, the inventor etc. have also carried out research repeatedly to the auxiliary direction beyond above-mentioned crystal face, have determined thus the auxiliary direction that is conducive to resistance to bending.

That is to say, for example, 013} face, 023} face or there is the crystal orientation approaching with these crystal faces, particularly, be with these crystal faces in ± 10 left and right the crystal face with interior crystal orientation, there is the effect that improves resistance to bending.In addition, these crystal faces carry out after recrystallization in full annealed operation, and its crystal orientation can not change yet.Therefore,, for these crystal faces, if can control after final cold rolling process, the state of the rolled copper foil before full annealed operation, can give excellent resistance to bending to rolled copper foil.

But { 013} face, { even if 023} face is present on the rolling surface of rolled copper foil, in the X-ray diffraction that adopts 2 θ/θ method is measured, inspection does not measure yet.Because copper is the crystal of face-centered cubic structure, therefore in the X-ray diffraction that adopts 2 θ/θ method is measured, if { h of hkl} face, k, l are not all odd number value or are not all even number value, can not show as diffraction peak.This be because, if { 013} face, { 023} face, h, k, l are that odd number value and even number value mix and exist to picture, because delustring principle can cause diffraction peak disappearance.

Therefore,, in present embodiment, use X ray utmost point figure method and stipulate these crystal faces according to above-mentioned formula (2).In foregoing, { diffraction peak of 111} face, { the 013} face that expression existence is parallel with the rolling surface of rolled copper foil when angle of inclination ψ is 47 °.In addition,, by average intensity of this diffraction peak etc., can know { the state of 013} face.In addition { diffraction peak of 111} face, { the 023} face that expression existence is parallel with the rolling surface of rolled copper foil when angle of inclination ψ is 53 °.In addition,, by average intensity of this diffraction peak etc., can know { the state of 023} face.

By making the straight line in the graphic representation of diffraction peak average intensity meet above-mentioned formula (2), the occupation rate that can form these crystal faces is high rolled copper foil fully, and can give excellent resistance to bending.Whether this straight line meets above-mentioned formula (2), the magnitude relationship of the magnitude relationship of the diffraction peak average intensity when diffraction peak average intensity when being 47 ° such as angle of inclination ψ is 53 ° with angle of inclination ψ, these average intensities and the peaked average intensity of graphic representation, is connected the decisions such as slope of the straight line of 2 average intensities.

In addition,, for giving resistance to bending this point to rolled copper foil by meeting the above-mentioned formula (2) of the graphic representation that uses diffraction peak average intensity, the inventor etc. investigate as follows.Can think, when { 013} face, { 023} face and the crystal orientation approaching with these crystal faces with the poor less crystal face of crystal orientation of these crystal faces, while existing with specified amount in rolled copper foil, have formed texture.And can think, by making these crystal faces form texture, contribute to the raising of resistance to bending.

The inventor etc. think, the condition that is 1/4th with respect to the maximum value [B] of graphic representation by the vertical axis intercept [A] of the straight line of above-mentioned graphic representation gained, represents whether these crystal faces form the border of texture.That is to say, during [A]/[B] <1/4, can think that { 013} face, { 023} face etc. does not form texture, or forms insufficiently, has not given play to above-mentioned effect.In addition, more high better by [A]/[B] of above-mentioned formula (2) defined, up to now, also do not confirm higher limit.

(about the surfaceness of formula (3), (4) regulation)

As mentioned above, the discoveries such as the inventor, except the control of the diffraction peak intensity of each crystal face being compared etc., when the surfaceness of the rolling surface of rolled copper foil is prescribed value when following, the resistance to bending that also can improve rolled copper foil.Its reason can be thought, if the concavo-convex difference of rolled copper foil rolling surface is larger,, when bending rolled copper foil, recess is out of shape to opening direction, easily produces and breaks with this as the starting point.

At first, 10 mean roughness Rzjis of use such as inventor carry out the surfaceness of regulation rolled copper foil.By controlling it as below prescribed value, can improve the resistance to bending of rolled copper foil.

Yet while only controlling 10 mean roughness Rzjis, there is deviation in the resistance to bending that has the coupons that each determination test uses, and cannot stably obtain the situation of excellent resistance to bending.

The inventor etc. have carried out further active research, found that, except 10 mean roughness Rzjis, by carrying out regulation surfaceness with arithmetic average roughness Ra, and they are controlled, can stably obtain excellent resistance to bending.The inventor etc., for this reason, in view of the index feature of the various surfacenesses shown in above-mentioned table 1, have carried out following investigation.

Maximum height Rz in JIS B0601:2001 shown in above-mentioned table 1 regulation is represented by protuberance and the difference of recess.Therefore,, even if other parts are how smooth, if there is outstanding larger part, the darker part of depression, maximum height Rz also becomes large.

As 10 mean roughness Rzjis of one of surfaceness index of the rolled copper foil of present embodiment, be to select to comprise this protuberance and respectively difference of 5 of recess the value of the gained that quantized.That is to say, owing to using summit and the lowest point to amount at 10, quantize, can as above-mentioned maximum height Rz, not be only therefore 1 concavo-convex poor, it can obtain has the information of the concavo-convex difference as which on average.

On the other hand, as the arithmetic average roughness Ra of another index of rolled copper foil surfaceness, and be conceived to the differences such as 10 mean roughness Rzjis of concavo-convex difference, it is conceived to there are on the whole how many fluctuatings measuring position.That is to say, roughness curve has departed from how many with respect to the linearity average line as center, has found out the area of concavo-convex of average as a whole average line and roughness curve.Therefore, even if maximum height Rz is larger, if only have the outstanding larger part in a place etc., the situation that also has arithmetic average roughness Ra to diminish.In addition,, even the rolled copper foil that each 5 points of maximum jog are roughly the same and 10 mean roughness Rzjis are equal to each other each other, if there is surface irregularity etc. in other parts, also there is arithmetic average roughness Ra to become large situation.On the contrary, if the surface irregularity of other parts in the scope of each 5 points of maximum jog, the situation that has arithmetic average roughness Ra to diminish.

According to the inventor etc., In view of the foregoing, by 10 mean roughness Rzjis are controlled in prescribed value, it is extremely large concavo-convex poor to get rid of, and jog cracking can suppress to bend rolled copper foil time, the situation of breaking.On the other hand, by arithmetic average roughness Ra is controlled in prescribed value, can suppress deviation as a whole, and then can realize the stabilization of resistance to bending numerical value.

As mentioned above, according to present embodiment, the rolled copper foil internal control showing by such X-ray diffraction peak of 2 θ/θ method, X ray utmost point figure method etc., can give excellent resistance to bend(ing) and resistance to bending to rolled copper foil.In addition, the external control of the rolled copper foil that surfaceness by 10 mean roughness Rzjis and arithmetic average roughness Ra etc. shows, can stably give more excellent resistance to bending to rolled copper foil.

(3) manufacture method of rolled copper foil

Then, use Fig. 1 to describe the manufacture method of the rolled copper foil of one embodiment of the present invention.Fig. 1 means the schema of manufacturing process of the rolled copper foil of present embodiment.

(the preparatory process S10 of ingot bar)

As shown in Figure 1, first, the fine copper such as oxygen free copper (OFC:Oxygen-Free Copper), tough pitch copper of usining are cast as starting material, and preparation ingot bar (ingot casting, ingot).Ingot bar for example forms has the tabular of specific thickness, Rack.Also can form the lower concentration copper alloy of the interpolation material that has added regulation in order to adjust the various characteristics of rolled copper foil in as fine copper such as raw-material oxygen free copper, tough pitch coppers.

The various characteristics that the enough interpolation materials of energy are adjusted, for example, have thermotolerance.As mentioned above, the rolled copper foil of using for FPC, gives the full annealed operation of high resistance to bend(ing) to rolled copper foil and carries out together with the operation of for example fitting with FPC substrate.Heating temperature during laminating, such as according to being set by the solidification value of the formed base materials such as resin, the solidification value of caking agent used etc. of FPC, a wider range of temperature condition and varied.For the softening temperature of rolled copper foil is adapted with the Heating temperature of so setting, sometimes need to add to regulate the stable on heating interpolation material of rolled copper foil.

As ingot bar used in present embodiment, in following table 2 illustration do not add material ingot bar, added the ingot bar of the interpolation material of several types.

[table 2]

In addition, as the interpolation material shown in table 2, other adds material, for improving or reducing stable on heating interpolation material, for example, there is the example of any one or more element in boron (B), niobium (Nb), titanium (Ti), nickel (Ni), zirconium (Zr), vanadium (V), manganese (Mn), hafnium (Hf), tantalum (Ta) and the calcium (Ca) about interpolation 10ppm～500ppm.Or there is the Ag of interpolation to add element as the 1st, and add any one or more element of these elements cited in typical example as the example of the 2nd interpolation element.In addition, can also add micro-chromium (Cr), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), gold (Au) etc.

In addition, the composition of ingot bar also can roughly maintain former state in the rolled copper foil after final cold rolling process S40 described later, and added material in ingot bar in the situation that, ingot bar and rolled copper foil have roughly the same interpolation material concentration.

In addition, the temperature condition of annealing operation S32 described later suitably changes according to the thermotolerance of copper material, interpolation material.But, such copper material, add material, the change of the temperature condition of the annealing operation S32 that adapts with it etc., for the effect of present embodiment, almost do not affect.

(hot-rolled process S20)

Then, ready ingot bar is implemented to hot rolling, form the thinner sheet material of specific thickness after thickness ratio casting.

(repeating operation S30)

Then, repeat to implement cold rolling process S31 and the annealing operation S32 of stipulated number, carry out repetition operation S30.That is to say, to having implemented sheet material cold rolling and work hardening, implement anneal, by sheet material annealing, thereby relax work hardening.By being repeated stipulated number, can be called as the copper bar of " blank ".In copper product, added while regulating stable on heating interpolation material etc., according to the thermotolerance of copper product, suitably changed the temperature condition of anneal.

In addition, in repeating operation S30, the annealing operation S32 in repetitive process is called " process annealing operation ".In addition, last by repetitive process, is called " final annealing operation " or " blank anneal operation " at the annealing operation S32 that is about to carry out carrying out before final cold rolling process S40 described later.In blank anneal operation, copper bar (blank) is implemented to blank anneal and process, obtain the blank of annealing.In blank anneal operation, changing temperature condition according to the thermotolerance of copper product and suitably.At this moment, blank anneal operation preferably at the temperature condition that can fully relax the processing strain causing because of above-mentioned each operation, for example, is processed under roughly the same temperature condition and is implemented with Full Annealing.

(final cold rolling process S40)

Then, implement final cold rolling process S40.Final cold rolling cold rolling also referred to as precision work, by annealing blank is repeatedly implemented, as accurately machined cold rolling, to form thin Copper Foil shape.At this moment, in order to obtain having the rolled copper foil of high resistance to bend(ing), it is more than 90% making total degree of finish, and more preferably more than 94%.Thus, after full annealed operation, form the rolled copper foil that easily obtains more excellent resistance to bend(ing).

And, as mentioned below, by controlling the degree of finish of multiple cold rolling every 1 time (1 passage),, move the position of neutral point and the surfaceness of the roller that rolling is used etc., and change stress under compression and the tensile stress that acts on annealing blank when cold rolling.Thus, can change the diffraction peak intensity ratio of each crystal face of rolled copper foil.

That is to say, the degree of finish of every 1 passage, preferably along with repeatedly cold rolling, annealing blank attenuation and slowly reducing., for the degree of finish of every 1 passage, copy the example of above-mentioned total degree of finish herein, the thickness of the workpiece before the rolling of n passage is being made as to T _bn, the thickness of the workpiece after rolling is made as to T _antime, by degree of finish (the %)=[(T of every 1 passage _bn-T _an)/T _bn] * 100 represent.

The workpieces such as rolling adds man-hour, annealing blank, by being for example incorporated in the gap between 1 pair of Rolling roller opposite to one another, and draw and attenuation from opposition side.The speed of workpiece, the inlet side before being incorporated into Rolling roller is slower than the speed of rotation of Rolling roller, faster than the speed of rotation of Rolling roller at the outlet side from Rolling roller is drawn.Therefore, at inlet side, workpiece is applied to stress under compression, at outlet side, workpiece is applied to tensile stress.For workpiece is processed to attenuation, should make stress under compression > tensile stress.By regulating the degree of finish of every 1 passage, the stress under compression > tensile stress of can take is prerequisite, adjusts the ratio of each stress component (compression component and stretching composition).

In addition,, in final cold rolling process S40, preferably according to often repeatedly cold rolling, the mode that below position of the neutrality point of explanation will be moved to the outlet side of Rolling roller is controlled.As mentioned above, the speed at inlet side and outlet side with respect to the magnitude relationship of Rolling roller speed of rotation workpiece conversely, certain position between inlet side and outlet side and the speed of rotation of Rolling roller equate.The equal position of the two speed is called to neutral point, maximum to workpiece applied pressure at neutrality point.

The position of neutral point can be by adjustment the place ahead tension force, rear tension force, roll speed (speed of rotation of Rolling roller), Rolling roller diameter, Rolling roller the combination of surfaceness, degree of finish, rolling loading etc. control.That is to say, by controlling the position of neutral point, also can adjust the ratio of stress under compression and tensile stress.

In addition,, in final cold rolling process S40, preferably use surfaceness to count the Rolling roller below 0.075 μ m with arithmetic average roughness Ra.The surfaceness of Rolling roller is influential to the surfaceness of the stress equilibrium of above-mentioned stress under compression and tensile stress, rolled copper foil.Therefore,, by being prescribed value by the Roughness Surface on Control of Rolling roller, can control the ratio of each crystal face.In addition, can obtain the rolled copper foil that surfaceness meets above-mentioned formula (3), (4).

In addition, at this moment, preferably, after suitably adjusting oil film equivalent, make the surfaceness of Rolling roller reach prescribed value.Oil film equivalent is the index relevant with the oil film thickness of the ROLLING OIL being coated with on workpiece.For oil film equivalent, as described below.

Degree of finish by every 1 passage of stress under compression during final cold rolling process S40 and the stress equilibrium of tensile stress is, move the position of neutral point, the surfaceness of Rolling roller etc. is controlled.Stress under compression when in addition, the balance of the diffraction peak intensity of each crystal face is mainly by final cold rolling process S40 and the stress equilibrium of tensile stress determine.

Specifically, in the rolling of final cold rolling process S40 etc., add man-hour, the copper crystal in copper product produces rotation phenomenon because of the stress that rolling adds man-hour, and by some paths and to { 022} face changes.Stress under compression is larger, more easily passes through that { 013} face, { 023} face, tensile stress is larger, more easily passes through { 111} face.Then, respectively to { 022} face changes.Do not arrive though the crystal of 022} face arrive 022} face due to tensile stress to { crystal of 111} face rotation, becomes secondary orientation.

By the stress equilibrium of such change stress under compression and tensile stress, to { path changing that 022} face changes can be adjusted the balance of diffraction peak intensity of the crystal face in secondary orientation.The balance of the diffraction peak intensity of this crystal face, as mentioned above, has a huge impact the resistance to bend(ing) of rolled copper foil, resistance to bending.

As mentioned above, by carrying out size control, the position control of neutral point, the control of the surfaceness of Rolling roller etc. of the degree of finish in each passage, and implement final cold rolling process S40 simultaneously, can be met the rolled copper foil of above-mentioned formula (1), (2).In addition, the above-mentioned surfaceness by 10 mean roughness Rzjis and arithmetic average roughness Ra defined is prescribed value.Therefore,, after full annealed operation, can obtain possessing the high resistance to bend(ing) of the alternating bending of bearing simultaneously and bearing compared with the rolled copper foil of the excellent resistance to bending of small-bend radius.

(surface treatment procedure S50)

To form the blank of Copper Foil shape through above operation, implement the surface treatment of regulation.By above operation, manufacture the rolled copper foil of present embodiment.

(4) manufacture method of flexibility printed circuit board

Then, the manufacture method of the flexibility printed circuit board (FPC) of the rolled copper foil of use one embodiment of the present invention is described.

(full annealed operation (CCL operation))

First, the rolled copper foil of present embodiment is cut to specified dimension, and with such as being fitted by the base material of the formed FPC of resin such as polyimide, form CCL(copper clad laminate, Copper Clad Laminate).At this moment, can adopt the method for the 3 layers of material CCL of formation that fit by caking agent and any not by caking agent but in the method for the formation 2 material layer CCL that directly fit.When using caking agent, by heat treated, caking agent is solidified, and make rolled copper foil and base material closely sealed and carry out integrated.When not using caking agent, by heating and pressurizing, make rolled copper foil and base material directly closely sealed.Heating temperature, time can suitably be selected according to the solidification value of caking agent, base material etc., for example, at the more than 150 ℃ temperature below 400 ℃, can be made as 1 minute above below 120 minutes.

As mentioned above, the thermotolerance of rolled copper foil is adjusted according to Heating temperature at this moment.Therefore, by the heating in CCL operation, the softening also recrystallization of rolled copper foil.That is to say, the CCL operation that rolled copper foil is fitted on base material is held a concurrent post the full annealed operation to rolled copper foil.By rolled copper foil is implemented to full annealed operation, can obtain having the rolled copper foil of recrystallization tissue.

That is to say, before full annealed operation as main orientation 022} face and as secondary orientation { great majority of 002} face form together by { the 002} face of the modified crystal structure of attaching most importance to.Thus, can obtain high resistance to bend(ing).

In addition, other secondary orientation also by the modified crystal structure of attaching most importance to, and has kept the state after final cold rolling process after recrystallization, does not almost change.By forming recrystallization state, the crystal face in these secondary orientation is eliminated the impact of work hardening, and the work that the crystal face in these secondary orientation has shows in order to approach form to greatest extent.

For example, can bring into play { 013} the face, { effect of the resistance to bending of raising that 023} face has.At this moment, due to { 013} face and { 023} face is because the condition that obtains from above-mentioned formula (2) is in the abundant high state of occupation rate, so its effect shows significantly.

In addition, by making to become prescribed value by the surfaceness of above-mentioned 10 mean roughness Rzjis and arithmetic average roughness Ra defined, deviation is less, can stably obtain excellent resistance to bending.

In addition, as mentioned above, by making CCL operation, hold a concurrent post full annealed operation, in operation before rolled copper foil is fitted on base material, under state after can the work hardening after cold rolling process, process rolled copper foil, and can be not easy to cause the distortion such as elongation when rolled copper foil is fitted on base material, fold, bending.

Each crystal face in secondary orientation does not almost change before and after full annealed operation.Therefore, in order to obtain resistance to bend(ing) and resistance to bending, as long as the rolled copper foil after final cold rolling process, before full annealed operation is controlled to secondary orientation so that it meets above-mentioned relation formula, condition.

(surface working operation)

Then, the rolled copper foil being fitted on base material is implemented to surface working operation.In surface working operation, carry out following operation: the protective membrane that uses the distribution that forms copper wiring etc. such as methods such as etchings on rolled copper foil to form operation, implements the surface-treated surface treatment procedures such as plating processing in order to improve the connection reliability of copper wiring and other electronic unit and form the protective membranes such as solder resist in order to protect copper wiring etc. in the mode of the part on covering copper distribution forms operation.

By above operation, manufacture the FPC of the rolled copper foil that uses present embodiment.

< other embodiment of the present invention >

Above, embodiments of the present invention are illustrated, but the present invention is not limited to above-mentioned embodiment, and can in the scope that does not depart from its main idea, carries out various changes.

For example, in the above-described embodiment, mainly use Ag as regulating the stable on heating interpolation material of rolled copper foil, but adding material is not limited to cited material in Ag, above-mentioned typical example etc.In addition, the various characteristics that can regulate by interpolation material is not limited to thermotolerance, and the various characteristics that can regulate as required suitably selects to add material.

In addition, the CCL operation in ，FPC manufacturing process is held a concurrent post the full annealed operation to rolled copper foil in the above-described embodiment, but full annealed operation also can be used as the operation different with CCL operation, carries out.

In addition, in the above-described embodiment, rolled copper foil is used to FPC purposes, but the purposes of rolled copper foil is not limited thereto, can also be for needing the purposes of resistance to bend(ing) and resistance to bending.For the thickness of rolled copper foil, according to the various uses with headed by FPC purposes, can or surpass 20 μ m etc. for ultra-thin below 10 μ m.

In addition, in the above-described embodiment, making total degree of finish in final cold rolling process S40 is 90% with first-class, to obtain excellent resistance to bend(ing), but the method that obtains resistance to bending by adjusting the crystal face in secondary orientation can be used independently with it.That is to say, in resistance to bending particularly important, and obtained in situation that resistance to bend(ing) to a certain degree gets final product etc., also can make the total degree of finish in final cold rolling process, such as 85%, 75%, 65% etc., less than 90%.

In addition, in the above-described embodiment, { the 013} face and { during 023} face, in X ray utmost point figure method, measure by reflection method especially, but also can measure by transmission method detecting.In addition,, except X ray utmost point figure method, can also adopt inverse pole figure (Inverse Pole-Figure, antipole point diagram) method, other method.

In addition, in order to play effect of the present invention, above-mentioned operation differs, and to establish a capital be necessary.Various conditions cited in above-mentioned embodiment, aftermentioned embodiment are also illustration, can suitably change.

Embodiment

Then,, for embodiments of the invention, together describe with comparative example.

(1) use the rolled copper foil of oxygen free copper

First, the embodiment 1～4 of oxygen free copper and the rolled copper foil of comparative example 1～7 are used in making as described below, and respectively they are carried out to various evaluations.

(making of rolled copper foil)

The oxygen free copper of the Ag that aimed concn is 200ppm has been added in use, according to making the rolled copper foil of embodiment 1～4 and comparative example 1～7 with above-mentioned embodiment same step and method.But, for comparative example 1～7, mainly in final cold rolling process, comprise the processing that makes the degree of finish of every 1 passage described later, the position of neutral point, the surfaceness of Rolling roller etc. depart from formation etc.

Specifically, prepare in oxygen free copper, to dissolve the Ag of specified amount and the thickness cast is the ingot bar that 150mm, width are 500mm.In following table 3, represent to analyze by high-frequency inductive coupling plasma body (ICP:Inductively Coupled Plasma) Emission Spectrophotometer method the analytical value of Ag concentration that obtain, in ingot bar.

[table 3]

As shown in table 3, for aimed concn 200ppm, analytical value is 183ppm～218ppm, is all controlled as 200ppm ± 20ppm(10%) deviation in degree.Except the situation that Ag contains a few ppm～tens ppm left and right as inevitable impurity originally in as main raw-material oxygen free copper, the a variety of causes such as deviation during because of cast billets, the deviation with respect to aimed concn in ± 10% degree is normal conditions in metal material field.

Then, by the step and method same with above-mentioned embodiment, by hot-rolled process, obtain after sheet material that thickness is 8mm, repeat to implement cold rolling process and at the temperature of 750 ℃～850 ℃, keep the process annealing operation of approximately 2 minutes, making thickness is 0.4mm(400 μ m) copper bar (blank).Then, by keeping the blank anneal operation of approximately 1 minute to obtain the blank of annealing at the temperature of approximately 750 ℃.

Herein, temperature condition of each annealing operation etc. adapts with the thermotolerance of the oxygenless copper material that contains 183ppm～218ppm Ag.In addition, for forming identical copper product, using different temperature condition in each annealing operation, is because the thickness of thermotolerance along with copper product changes, and when copper product is thinner, can reduce temperature.

Finally, according to carrying out final cold rolling process with the same step and method of above-mentioned embodiment.Condition in final cold rolling process is as shown in table 4 below.

[table 4]

* the length from outlet side end to neutrality point of Rolling roller and workpiece contact surface

As shown in table 4, along with from epimere to hypomere thickness of slab successively attenuation, each embodiment, comparative example be conversion condition as shown in right hurdle separately all, carries out finally cold rolling.That is to say, changing thickness is the position of degree of finish and the neutral point of every 1 passage in the cold rolling processing below 400 μ m.The position of the neutrality point shown in right hurdle (mm) separately, represents by Rolling roller and the length from outlet side end to neutrality point of contact surface as the annealing blank of workpiece.

Each embodiment, comparative example be selection condition in the scope on right hurdle separately all, for each embodiment, implements respectively to process to reach in the scope that regulation forms, and in addition for each comparative example, implements respectively to process to depart from the formation of regulation.But the condition of table 4 current used is an example, in what kind of thickness of slab down conversion condition, how to set the numerical value of each condition, can be according to suitably selections such as the crystalline structure of final desirable rolled copper foil.As shown in the condition of comparative example, in general, if carry out attenuate slowly, there is the tendency that departs from this formation.

In addition, by arithmetic average roughness Ra be Rolling roller that surfaceness below 0.075 μ m is little for embodiment 1～4, by arithmetic average roughness Ra, be that Rolling roller that more than 0.080 μ m surfaceness is large is for comparative example 1～7.

In addition,, in order to obtain excellent resistance to bend(ing), under the top and bottom of embodiment 1～4 and comparative example 1～7, it is more than 94% imposing a condition and making the total degree of finish in final cold rolling process.Specifically, in embodiment 1～4 and comparative example 1～7, all making total degree of finish is 97%.By upper, making thickness is the embodiment 1～4 of 12 μ m and the rolled copper foil of comparative example 1～7.

Then, each rolled copper foil of as above making is carried out to following evaluation.

(using the X-ray diffraction of 2 θ/θ method to measure)

First, use 2 θ/θ method to carry out X-ray diffraction mensuration to the rolled copper foil in embodiment 1～4 and comparative example 1～7.For the detailed content of measuring method, use Fig. 2 to describe as follows.Fig. 2 means the figure of the X-ray diffraction measuring method summary in embodiments of the invention and comparative example.

As shown in Figure 2, the rolled copper foil coupons 50 in embodiment 1～4 and comparative example 1～7 being configured to as mentioned above can be around θ axle, ψ axle, these 3 the scan axis rotation of φ axle.These 3 scan axises are called turning axle in sample axle, tilting axis, face conventionally.In the X-ray diffraction of present embodiment is measured, use the X ray (Cu K α line) being produced by copper (Cu) pipe ball.

In the X-ray diffraction that uses 2 θ/θ method is measured, with respect to incident X-rays, with θ axle scanning (around the rotation of θ axle) coupons 50 and not shown detector.At this moment, making the sweep angle of coupons 50 is angle θ, and the sweep angle that makes detector is angle 2 θ.Thus, as mentioned above, with angle, θ injects incident X-rays, and detects the diffraction X ray with angle 2 θ diffraction.

In the present embodiment and comparative example, the X-ray diffraction device (model: Ultima IV), and carry out this mensuration under the condition shown in following table 5 of using Co., Ltd. Neo-Confucianism to manufacture.As representative, in Fig. 3 (a) and (b), represent the X-ray diffractogram of embodiment 1,2, in Fig. 3 (c), represent the X-ray diffractogram of comparative example 3.

[table 5]

Then, by { 022} face, { 002} face, { 113} face, { the 111} face and { it is 100 ratio that the diffraction peak intensity of 133} face is converted into aggregate value, obtains the diffraction peak intensity ratio of each crystal face of the copper crystal of measuring by 2 θ/θ method.In addition obtain, the value (I of above-mentioned formula (1)?<022}+ I?<002}).For the rolled copper foil of embodiment 1～4 and comparative example 1～7, in following table 6, represent to compare I as the diffraction peak intensity of each crystal face obtained above?<022}, I?<002}, I?<113}, I?<111}and I?<133}value, and the value of formula (1).

[table 6]

*I _{022}+I _{002}+I _{113}+I _{111}+I _{133}=100

As mentioned above, in the present embodiment and comparative example, change the degree of finish of every 1 passage in final cold rolling process, the position of neutral point.In addition,, in embodiment and comparative example, change the surfaceness of Rolling roller.Thus, cold rolling, add man-hour, be applied to compression component on workpiece and the stress component ratio of stretching composition and change.The ratio of each crystal face of result changes, and the diffraction peak intensity ratio of each crystal face shown in table 6, the value of formula (1) have also produced variation.

In addition, as shown in table 6, in the combination of each condition of embodiment 1～4, the value of formula (1) is all in above-mentioned specialized range.

On the other hand, in the combination of each condition of comparative example 1～7, in some rolled copper foils, the value of formula (1) drops on outside above-mentioned specialized range.In table 6, by dropping on the extraneous value of afore mentioned rules, with the boldface letter with underscore, represent.

(mensuration of using X ray utmost point figure method to carry out)

Then, by X ray utmost point figure method, the rolled copper foil of embodiment 1～4 and comparative example 1～7 is measured.In this measuring method, have that to make angle of inclination ψ described later be the reflection method of 15 °～90 ° of scopes and be the transmission method of 0 °～15 ° of scopes.In the present embodiment, and above-mentioned embodiment is same, uses reflection method.For the detailed content of measuring method, use Fig. 2 to describe as follows.

As shown in Figure 2, in using the mensuration of X ray utmost point figure method, and the X-ray diffraction of above-mentioned use 2 θ/θ method is measured the coupons 50 that similarly configures each rolled copper foil.

In addition,, in X ray utmost point figure method, use the angle of inclination ψ of following regulation to measure.That is to say, the angle of inclination ψ of the direction vertical with coupons 50 (φ direction of principal axis) is defined as to 90 °.In addition, using as geometrically corresponding to paid close attention to crystal face { crystal face of hkl} face { h ' k ' l ' } face with { the formed angle of hkl} face is made as ψ '.At this moment, regulation angle of inclination ψ=90-ψ '.

Such basis for establishing is coupons 50 to be carried out to ψ axle scanning (around the rotation of ψ axle), and angle of inclination ψ more than 15 ° is being changed in the scope below 90 °.That is to say, with the angle of inclination ψ inclined test print 50 in above-mentioned scope.Make as mentioned above on one side angle of inclination ψ change, on one side under a plurality of angle of inclination ψ, and 2 θ/θ method detection of diffracted X ray similarly.That is to say, when angle of inclination ψ is 90 °, carry out in principle and the same mensuration of 2 θ/θ method.

In addition, when carrying out the mensuration of each angle of inclination ψ, the sweep angle of detector is fixed as to angle 2 θ, with respect to the 2 θ values of { h ' k ' l ' } face, coupons 50 is carried out to φ axle scanning (around the rotation of φ axle), and face internal rotation angle degree φ more than 0 ° is being changed in the scope below 360 °.That is to say, make coupons 50 carry out rotation with the face internal rotation angle degree φ in above-mentioned scope.For the diffraction peak of { h ' k ' l ' } face of mensuration like this, each angle of inclination ψ is obtained to the average intensity that face internal rotation angle degree φ is 0 ° of diffraction peak in above 360 ° of following scopes.

At this moment, { h ' k ' the l ' } face detecting under the angle of inclination ψ of regulation, it is parallel with rolling surface with rolled copper foil that { hkl} face is corresponding geometrically.To pay close attention in the present embodiment { hkl} face is { 013} face and { 023} face.It is parallel with rolling surface with rolled copper foil that { face that 013} face is geometry corresponding relation detects { 111} face when angle of inclination ψ is 47 °.It is in addition, parallel with rolling surface with rolled copper foil that { face that 023} face is geometry corresponding relation detects { 111} face when angle of inclination ψ is 53 °.

Therefore, as mentioned above, by use X ray utmost point figure method gained { graphic representation of the diffraction peak average intensity of 111} face can judge whether the rolled copper foil of the present embodiment possesses the crystalline structure of regulation.

In the present embodiment and comparative example, the X-ray diffraction device (model: Ultima IV), carry out said determination under the condition shown in following table 7 of using Co., Ltd. Neo-Confucianism to manufacture.In Fig. 4～7, represent to draw { the graphic representation of the diffraction peak average intensity made of 111} face in embodiment 1～4.In addition,, in Fig. 8～14, represent to draw { the graphic representation of the diffraction peak average intensity made of 111} face in comparative example 1～7.

[table 7]

Setting item	Condition
		Anticathode (target)	Cu
Tube voltage	40kV
		Tube current	40mA
Mode determination	Utmost point figure
		2 θ fixed angles	43.3°
The step of angle of inclination ψ is wide	1 ° or 2 °
		The step of ψ=0～360 ° scanning is wide	1°
ψ=0～360 ° sweep velocity	360 °/minute
		Specimen size	About 50mm * about 50mm

The graphic representation transverse axis of Fig. 4～14 be angle of inclination ψ (°), the longitudinal axis is diffraction peak intensity (arbitrary unit).In the drawings, draw and have each average intensity by using the mensuration of above-mentioned X ray utmost point figure method to obtain.In addition, show in the drawings { maximum value [B] of the diffraction peak average intensity of 111} face and 1/4th the value thereof within the scope of graphic representation.And, show in the drawings { straight line of the diffraction peak average intensity of 111} face and vertical axis intercept [A] thereof when connecting angle of inclination ψ is respectively 47 °, 53 °.

As shown in Fig. 4～14, in the result of embodiment 1～4, vertical axis intercept [A] is all the more than 1/4th of graphic representation maximum value [B], meets above-mentioned formula (2).In addition,, in comparative example 1,2, be also met the graphic representation of formula (2).On the other hand, in the result of comparative example 3～7, vertical axis intercept is peaked 1/4th less than graphic representation, does not meet above-mentioned formula (2).

(surface roughness measurement)

Then,, in order to understand the surfaceness of the rolled copper foil of embodiment 1～4 and comparative example 1～7, carry out the mensuration of 10 mean roughness Rzjis and arithmetic average roughness Ra.In this is measured, the surface roughness measurement device (model: SE500) of using little Ban institute of Co., Ltd. to manufacture.As condition determination, be made as: contact pilotage diameter is 2 μ m, and finding speed is 0.2mm/sec, and measured length is 4mm, and the datum length of choosing is 0.8mm, and loading is below 0.75mN.Measurement result is shown in to following table 8.

[table 8]

?	Rzjis（μm）	Ra（μm）	?	Rzjis（μm）	Ra（μm）
						Embodiment-1	0.59	0.21	Comparative example-1	1.25	0.15
Embodiment-2	0.95	0.11	Comparative example-2	1.09	0.33
						Embodiment-3	0.78	0.30	Comparative example-3	1.43	0.11
Embodiment-4	0.75	0.12	Comparative example-4	1.99	0.21
						?	?	?	Comparative example-5	1.32	0.25
?	?	?	Comparative example-6	1.47	0.44
						?	?	?	Comparative example-7	1.08	0.20

As mentioned above, in the present embodiment and comparative example, in final cold rolling process, use respectively surfaceness, i.e. the different Rolling roller of arithmetic average roughness Ra.Therefore, as shown in table 8, in the combination of embodiment 1～4 each condition, the surface of rolled copper foil is compared with planarization, and 10 mean roughness Rzjis and arithmetic average roughness Ra are in above-mentioned specialized range.

On the other hand, in comparative example, although only two of comparative example 7 kinds of surfacenesses, in prescribed value, in the rolled copper foil of comparative example 1～6 in addition, are all that the value of one or both surfacenesses drops on outside above-mentioned specialized range.In table 8, by dropping on the extraneous value of afore mentioned rules, with the boldface letter with underscore, represent.

(evaluation of resistance to bend(ing))

Then,, in order to study the resistance to bend(ing) of each rolled copper foil, measure each rolled copper foil repeated flex until the flexible life test of the number of times (number of bends) of fracture.This test is used the FPC high speed bend test machine that Engineering Co., Ltd. of SHIN-ETSU HANTOTAI manufactures (model: SEK-31B2S), and according to the printed wiring industry meeting of the IPC(U.S.) standard to carry out.Figure 15 represents also to comprise the mode chart of the routine slip bend test device 10 of the FPC high speed bend test machine that Engineering Co., Ltd. of SHIN-ETSU HANTOTAI manufactures etc.

First, copying above-mentioned full annealed operation, is the coupons 50 of 12 μ m for the thickness that the rolled copper foil of embodiment 1～4 and comparative example 1～7 is cut into wide 12.5mm, long 220mm, implements the full annealed of 300 ℃, 60 minutes.In the CCL operation that this condition has been imitated at flexibility printed circuit board, an example of the actual heat being subject to of rolled copper foil when closely sealed with base material.

Then, as shown in figure 15, with screw 12, the coupons of rolled copper foil 50 is fixed on the sample retaining plate 11 of slip bend test device 10.Then, make coupons 50 contact and adhere to each other with vibration transfer part 13, by vibration driving body 14, make to vibrate transfer part 13 and vibrate on above-below direction, to coupons 50 transmitting vibrations, implement flexible life test.As the condition determination of flexible life, making bending radius 10r is 1.5mm, and stroke 10s is 10mm, and amplitude number is 25Hz.Under this condition, respectively 5 of the coupons 50 that mensuration scales off from each rolled copper foil, and relatively until there is the mean value of the number of bends of fracture.Show the result in following table 9.

[table 9]

As shown in table 9, in embodiment 1～4 and comparative example 1,2,4,6, all meet above-mentioned formula (1), therefore having obtained number of bends is 2,000,000 above high resistances to bend(ing).On the other hand, in not meeting the comparative example 3,5,7 of above-mentioned formula (1), be all that number of bends is significantly lower than the result of 2,000,000 times.

Even what should pay close attention to is comparative example 3,5,7, also there is the resistance to bend(ing) this point of higher level originally herein.This is to be more than 94% owing to having passed through the total degree of finish that has obtained real achievement in such as above-mentioned patent documentation 3 grades, the final cold rolling process that total degree of finish is 97% specifically.In embodiment 1～4, by making it further meet above-mentioned formula (1), can further improve resistance to bend(ing).

(evaluation of resistance to bending)

Then, study the resistance to bending of each rolled copper foil.In the common touchstone of relevant resistance to bending, do not carry out such as for the stdn of bending of desired 180 ° in FPC purposes etc.Therefore, by the method shown in Figure 16, measure until produce the cripping test of the bending number of times breaking on each rolled copper foil.

That is to say, first, for the coupons 50 that the rolled copper foil in embodiment 1～4 and comparative example 1～7 is cut into wide 15mm, long 100mm with respect to rolling direction, implement the full annealed of 300 ℃, 60 minutes.Then, as shown in figure 16, take sandwich the partition 20 that thickness is 0.15mm mode by 180 ° of coupons 50 bendings, and under this state with metal microstructure sem observation bending part, confirm to have crack-free.If do not broken, make rolled copper foil be back to stretched state originally from bending state.Using it as 1 circulation, for respectively 5 of the coupons 50 scaling off from each rolled copper foil, at each, circulate and observe bending part, recirculation is until generation is broken simultaneously, and mensuration bends number of times.Show the result in following table 10.

[table 10]

As shown in table 10, meet at the same time in the embodiment 1～4 of above-mentioned formula (2) and formula (3), (4), bending number of times is all more than 100 times, has obtained excellent resistance to bending.In addition, for these rolled copper foils, the deviation of the measurement result of above-mentioned 5 coupons 50 is less, has confirmed stably to obtain excellent resistance to bending.

On the other hand, in the arbitrary comparative example except comparative example 1,2, do not meet formula (2), and during bending number of times less than 100 times, can not get sufficient resistance to bending.This is also same for the comparative example 7 that meets the value of two kinds of surfacenesses.That is to say, for improving resistance to bending by control surface roughness, meeting formula (2) is prerequisite.But for the comparative example 1,2 that only meets formula (2), bending number of times is reluctantly for 100 times when above, although poor for embodiment, compare how many visible improvement with other comparative examples.

In following table 11, gather the above results that represents each rolled copper foil.In table, the situation that meets prescribed condition being designated as to zero, the situation outside condition of dropping on is designated as *.The result of resistance to bending is better than other comparative example, poorer than embodiment comparative example 1,2 is designated as △.

[table 11]

As mentioned above, by the value of above-mentioned formula (1) is positioned in prescribed value, that is to say, by the material from rolled copper foil or the relevant inside viewpoints such as crystal orientation that comprise secondary orientation, control, can give excellent resistance to bend(ing) to rolled copper foil.In addition, by the value of above-mentioned formula (2) and the surfaceness relevant with machinery or face shaping etc. is positioned in prescribed value, that is to say, by the viewpoint of inside and outside this two aspect from rolled copper foil, control, can stably to rolled copper foil, give excellent resistance to bending.

The rolled copper foil of embodiment 1～4 meets the value of above-mentioned any one, therefore aspect resistance to bend(ing), resistance to bending, is all demonstrating higher value, and is obtaining little, the stable resistance to bending of deviation.

On the other hand, comparative example 1,2 meets above-mentioned formula (1), (2) simultaneously, from inner viewpoint, controls.Yet they only meet a kind of value of surfaceness separately, from outside viewpoint, do not control.Therefore, although obtained excellent resistance to bend(ing), for resistance to bending, be, still the result poorer than embodiment.

In addition, comparative example 3～7 does not meet any one or both of above-mentioned formula (1), (2), and except comparative example 7, does not meet any one or both of surfaceness yet.Therefore, all insufficient in the either side of controlling from inner viewpoint and control from outside viewpoint.Therefore,, except meeting formula (1), only resistance to bend(ing), reluctantly beyond good comparative example 4,5, is all the poor result of resistance to bend(ing).In addition,, in any one of comparative example 3～7, result is all resistance to bending and comparative example 1,2 phase ratios.

(2) use the rolled copper foil of tough pitch copper

Then, use the tough pitch copper added the Ag that aimed concn is 200ppm, and be the embodiment 5,6 of 12 μ m and the rolled copper foil of comparative example 8～10 according to making thickness with the same step and method of above-described embodiment.But, for comparative example 8～10, comprise and make the condition of above-mentioned table 4, the surface irregularity of Rolling roller etc. depart from the processing of formation etc.

Ag concentration in the ingot bar of embodiment 5,6 and comparative example 8～10, in by the analytical value of IPC Emission Spectrophotometer method gained, is respectively 201ppm, 194ppm, 202ppm, 190ppm and 198ppm.With respect to aimed concn, be all the deviation in ± 10% degree, this is normal conditions in metal material field.In addition, according to the thermotolerance of the tough copper product that contains this concentration Ag, in process annealing operation and blank anneal operation, use the condition different with above-mentioned condition.Specifically, in process annealing operation, at the temperature of 650 ℃～750 ℃, keep approximately 2 minutes, in blank anneal operation, at the temperature of approximately 700 ℃, keep approximately 1 minute.In addition,, for these embodiment and comparative example, in final cold rolling process, be also suitable for the condition of above-mentioned table 4.

For the as above embodiment 5,6 of made and the rolled copper foil of comparative example 8～10, according to the step and method same with above-described embodiment, by 2 θ/θ method, carry out X-ray diffraction mensuration and use X ray utmost point figure method to measure, obtain above-mentioned formula (1), (2), and and the above-mentioned surfaceness of similarly measuring.

In addition,, after the rolled copper foil enforcement of embodiment 5,6 and comparative example 8～10 and above-mentioned same full annealed, the step and method according to same with above-described embodiment, carries out flexible life test and cripping test.

In following table 12, show the above results.In table 12, the value dropping on outside the specialized range of any one in above-mentioned formula (1)～(4) is represented with the boldface letter with underscore.

[table 12]

As shown in table 12, for the rolled copper foil of embodiment 5,6, meet formula (1), (2) simultaneously, and also meet the value of formula (3), (4).Therefore, result is that resistance to bend(ing), resistance to bending are all good.On the other hand, for the rolled copper foil of comparative example 8, only formula (2) drops on outside specialized range, and result is that resistance to bending is poor.In addition, for the rolled copper foil of comparative example 9, formula (1) and (2) are in specialized range, but surfaceness all drops on beyond prescribed value, and result is still that resistance to bending is poorer than embodiment.In addition, for the rolled copper foil of comparative example 10, all drop on beyond prescribed value under full terms, result is that resistance to bend(ing), resistance to bending are all poor.

As from the foregoing, if each condition all in specialized range,, for take tough pitch copper as main raw-material rolled copper foil, also can obtain good resistance to bending, and can realize the raising of resistance to bend(ing).

(3) use the different rolled copper foils that add material

Then, use has been added titanium (Ti) that Ag that aimed concn is 120ppm and aimed concn are 40ppm as the oxygen free copper that adds material, and is the embodiment 7,8 of 12 μ m and the rolled copper foil of comparative example 11～13 according to making thickness with the same step and method of above-described embodiment.But, for comparative example 11～13, comprise and make the condition of above-mentioned table 4, the surface irregularity of Rolling roller etc. depart from the processing of formation etc.

Ag concentration in the ingot bar of embodiment 7,8 and comparative example 11～13, in by the analytical value of IPC Emission Spectrophotometer method gained, is respectively 118ppm, 121ppm, 117ppm, 120ppm and 118ppm.In addition, Ti concentration is respectively 38ppm, 42ppm, 40ppm, 40ppm and 37ppm.With respect to aimed concn, be all the deviation in ± 10% degree, this is normal conditions in metal material field.

In addition,, according to the thermotolerance of the oxygenless copper material that contains this concentration Ag and Ti, in process annealing operation and blank anneal operation, use the condition different with above-mentioned condition.Specifically, in process annealing operation, at 650 ℃～750 ℃, keep approximately 2 minutes, in blank anneal operation, at the temperature of approximately 700 ℃, keep approximately 1 minute.In addition,, for these embodiment and comparative example, also in final cold rolling process, be suitable for the condition of above-mentioned table 4.

For the embodiment 7,8 of above-mentioned made and the rolled copper foil of comparative example 11～13, according to method and the step same with above-described embodiment, by 2 θ/θ method, carry out X-ray diffraction mensuration and use X ray utmost point figure method to measure, obtain above-mentioned formula (1), (2), and and the above-mentioned surfaceness of similarly measuring.

In addition,, after the rolled copper foil enforcement of embodiment 7,8 and comparative example 11～13 and above-mentioned same full annealed, according to method and the step same with above-described embodiment, carry out flexible life test and cripping test.

In following table 13, show the above results.In table 13, the value dropping on outside the specialized range of any one in above-mentioned formula (1)～(4) is represented with the boldface letter with underscore.

[table 13]

As shown in table 13, for the rolled copper foil of embodiment 7,8, the relation of the diffraction peak intensity of each crystal face meets formula (1), (2) simultaneously, and also meets the value of formula (3), (4).Therefore, result is that resistance to bend(ing), resistance to bending are all good.On the other hand, for the rolled copper foil of comparative example 11, only formula (1) drops on outside specialized range, and result is that resistance to bend(ing) is poor.In addition, for the rolled copper foil of comparative example 12, only formula (2) drops on outside specialized range, and result is that resistance to bending is poor.In addition, for the rolled copper foil of comparative example 13, due in surfaceness only arithmetic average roughness Ra drop on outside prescribed value, although therefore poor stability, resistance to bending is compared well with comparative example 12.

As from the foregoing, if each condition all in specialized range,, for having added the different rolled copper foils that add material such as Ag and Ti, can obtain good resistance to bend(ing) and resistance to bending.

The < inventor's etc. investigation >

The inventor etc. are to the control of crystal face in secondary orientation in the rolling Copper Foil manufacturing process and the investigation of the control of surfaceness, as described below.

(1) for crystallization, rotate

As mentioned above, in rollings such as final cold rolling process, add man-hour, copper product has been applied to stress under compression and than the tensile stress a little less than stress under compression.The stress that copper crystal in the copper product of rolling adds man-hour because of rolling produces to { the phenomenon of 022} face rotation, and along with the progress of rolling processing, the orientation of the crystal face parallel with rolling surface forms and is mainly { the rolling texture of 022} face.At this moment, as mentioned above, according to recently changing to { the path of 022} face rotation of stress under compression and tensile stress.To this, use Figure 17 to describe.

Figure 17 is the antipole point diagram of the fine copper shaped metal quoted from following technical literature (first), (a) mean the antipole point diagram of the crystallization sense of rotation producing by tensile deformation, (b) mean the antipole point diagram of the crystallization sense of rotation producing by compression set.In addition, in antipole point diagram, will { 002} face be denoted as that { 001} face, will { 022} face be denoted as { 011} face.That is to say, and 002} face by as with the minimum value of the face that 002} face is parallel 001} face represents, and 022} face by as with the minimum value of the face that 022} face is parallel { 011} face represents.

(first) editor, long Shima Shanxi one, " texture (collection closes Group Woven) ”，Wan Shan Co., Ltd., clear and on January 20th, 59, Fig. 2 .52(a of p96), (c)

As shown in figure 17, the copper crystal in copper product is when only producing distortion by tensile stress, to { rotation of 111} face, when only producing distortion by stress under compression, to { 011} face rotation.Rolling adds man-hour, and owing to producing compression component and being drawn into the distortion minute being harmonious, so crystallization sense of rotation is not so simple.But, because compression component is preponderated and produced distortion and be rolled processing than stretching composition, therefore generally speaking produce to { the crystallization rotation of 011} face, simultaneously according to the ratio of compression component and stretching composition, also can make part to { 111} face rotation.At this moment, because compression component is preponderated, therefore also produce to { crystallization of 111} face rotation turns back to { the crystallization rotation of 011} face.And in contrast, also oriented { { crystallization of 011} face is because stretching composition is to { 133} the face, { situation of 111} face rotation for the crystallization of 011} face rotation, arrival.

Like this, can think, when compression component and stretching composition keep the relation of compression component > stretching composition on one side, in mixing, deposit while producing during the course crystallization rotation on one side, the crystal face in final main orientation is { 011} face, in addition by compression component and stretching composition, mixed, and crystal face that the result of the crystallization rotation that causes is secondary orientation becomes { 001} face, { 113} face, { 111} face, { 133} face.

In addition, the crystal face as process in the crystallization rotation producing in stress under compression, has { 013} face, { 023} face etc.The crystal orientation of the antipole point diagram shown in Figure 18 is general situation, but in figure, has depicted { 013} face, { 023} face and the crystal face region less with the azimuth difference of these crystal faces.As shown in figure 18, in the crystallization that produces in stress under compression rotation, through { 013} face, { 023} is towards { 011} face ({ 022} face) rotation.

In rolling processing, as mentioned above, if not to the copper product of rolling apply stress under compression and than the tensile stress a little less than stress under compression the two, while cannot keep the shape of copper product to be rolled.That is to say, when only having stress under compression, the same with simple pressurization processing, can form the shape with radial expansion.Take stress under compression > tensile stress under prerequisite, and because rotation does not arrive, { impact of remaining, the tensile stress in the orientation of 022} face, to { crystallization of 111} face rotation becomes secondary orientation.Like this, reduce resistance to bending 111} face is by the formed secondary orientation of tensile stress, and improve resistance to bending { 013} face, { 023} face is by the formed secondary orientation of stress under compression.

Therefore, in order to suppress as much as possible in the rolling surface of rolled copper foil the occupation rate of 111} face, and improve as much as possible 013} face, the occupation rate of 023} face, on one side suitably adjust stress under compression and tensile stress balance to be rolled be on one side important.

(2) Characteristics Control of final cold rolling process

Compression component and stretching composition, as what carried out in the final cold rolling process S40 of above-mentioned embodiment, the rolling condition that for example can add by changing rolling every 1 passage in man-hour is controlled.That is to say, as attempted in above-mentioned embodiment, embodiment, for example, can be conceived to the variation of the degree of finish of every 1 passage.

In addition, in above-mentioned embodiment, embodiment, carry out the degree of finish of every 1 passage in final cold rolling process and controlled, also carried out the position control of neutral point simultaneously.That is to say, when adjusting the control parameter of compression component and stretching composition, for example, can also be conceived to the change in location of neutral point.

The controlling factor of the position of above-mentioned degree of finish, neutral point etc. is relevant with the structure of roller mill, and very broad aspect exists with ... the using method of roller mill.Specifically, due to the hop count of Rolling roller, the combining and configuring of the sum of Rolling roller, Rolling roller, the difference of the structure of the Rolling rollers such as the diameter of each Rolling roller, material, condition of surface (surfaceness) etc. can produce difference at aspects such as the stress under compression applying method to copper product, frictional coefficient.If roller mill is different, in above-described embodiment, the absolute value of each controlling factor of cited condition is also different, therefore can suitably adjust every kind of roller mill.In addition,, even identical roller mill, if the material of the condition of surface of Rolling roller, Rolling roller is different, the absolute value of each controlling factor is also different.Therefore, even identical roller mill also can suitably be adjusted according to state separately.

In above-mentioned embodiment, embodiment, also by the surfaceness of Rolling roller, control.For example, if the degree of finish of every 1 passage is fixed, change the surfaceness of Rolling roller, the frictional coefficient that the copper product being rolled is subject to changes, and the position of neutral point changes, and rolling loading also changes.Stress under compression in result rolling processing and the balance of tensile stress change, and the sense of rotation of copper crystal, rotate path change.

(3) Characteristics Control of being undertaken by the surfaceness of Rolling roller

As mentioned above, the discoveries such as the inventor, by the surfaceness with 10 mean roughness Rzjis and arithmetic average roughness Ra regulation rolled copper foil, and are controlled at them below prescribed value, can improve the resistance to bending of rolled copper foil.

So stably rolled copper foil is given the surfaceness of excellent resistance to bending, for example, can be controlled by the following factor of enumerating.That is to say, mainly contain the viscosities il of ROLLING OIL, the speed of rotation U of Rolling roller ₀, the speed U of copper product during rolling ₁, gripping angle α, average roll pressure p, Rolling roller surfaceness (arithmetic average roughness Ra) etc.In these factors, each factor beyond the arithmetic average roughness Ra of Rolling roller can gather as one as take the following formula (B) that following technical literature (second) is reference, as the oil film equivalent td corresponding to oil film thickness.

td={η（U ₀+U ₁）}/αp…（B）

(second) red bean island is bright, " about the surfaceness of the oil film thickness in rolling and roller and material ", Japanese mechanics meeting collection of thesis (the 3rd), 44 No. 377, volumes, clear and in January, 53, p332-339

As long as the oil film equivalent td of each factor defined except arithmetic average roughness Ra by Rolling roller can be kept to certain, just can alleviate the impact of these factors, thereby can only by the arithmetic average roughness Ra of Rolling roller, to the surfaceness of rolled copper foil, carry out various control.

Herein, the speed of rotation U of the Rolling roller of above-mentioned formula (B) ₀, the speed U of copper product during rolling ₁, average roll pressure p is also the degree of finish of every 1 passage under controlled rolling condition, the controlling factor of neutral point.When changing these controlling factors in order to control the degree of finish of every 1 passage, neutral point, for oil film equivalent td is kept to certain, for example, there is following methods.That is to say, for example, if by the viscosities il of ROLLING OIL 3 * 10 ^-3n/m ²s～5 * 10 ^-3n/m ²the scope internal control of s is made as necessarily, and gripping angle α is also certain.Thus, oil film equivalent td can be controlled as certain.

In the final cold rolling process S40 of above-mentioned embodiment, for example, after suitably adjusting oil film equivalent td, the surfaceness that makes Rolling roller is prescribed value, therefore can manufacture the rolled copper foil with regulation surfaceness.

In addition, in above-mentioned embodiment, embodiment, by the surfaceness of arithmetic average roughness Ra regulation Rolling roller, based on following reason.

That is to say, Rolling roller is in final cold rolling process S40, to use, relate to the important tool of copper product deformation processing.Therefore the integrality of, grasping as much as possible Rolling roller is everywhere very important.Therefore, by using, not on point, to grasp concavo-convex difference but the arithmetic average roughness Ra that grasps concavo-convex difference on face or line, thereby to have grasped the surfaceness of Rolling roller integral body.

In addition, the surfaceness that improves the rolled copper foil of resistance to bending can also be used other controlling factor to control.

(4) other controlling factor

In addition,, in above-mentioned embodiment, embodiment, according to the Rolling roller surfaceness comprising in final cold rolling process, at interior rolling condition, control sense of rotation, the rotate path of copper crystal, but also can carry out same control in other operation.

For example can think, by making the rolling condition of final cold rolling process, fix, and change the condition that is about to carry out final cold rolling process manufacturing process before, can also exert an influence to final cold rolling process, and indirectly change sense of rotation, the rotate path in final cold rolling process.But, if as above-mentioned embodiment, embodiment, change the rolling condition of final cold rolling process, can directly control sense of rotation, rotate path, and can further improve controlled.

Thus, the state of the crystal orientation of the rolled copper foil after final cold rolling process is not subject to the restriction of specific manufacture method.This be because, the state of the crystal orientation of rolled copper foil can be controlled by the whole bag of tricks, its method also exists multiple.

Claims

1. a rolled copper foil, is characterized in that, it is to possess major surfaces, and has the rolled copper foil after final cold rolling process, before full annealed operation with a plurality of crystal faces of described major surfaces in parallel,

Described a plurality of crystal face comprise 022} face, 002} face, 113} face, 111} face and 133} face,

To use 2 θ/θ method to carry out diffraction peak intensity that X-ray diffraction mensuration is obtained, that the aggregate value of take is 100 described each crystal faces that convert than being made as respectively I to described major surfaces?<022}, I?<002}, I?<113}, I?<111}and I?<133}time, I?<022}+ I?<002}>=75.0,

Use X ray utmost point figure method, for a plurality of angles of inclination in 15 ° of above 90 ° of following scopes, obtain respectively make the face internal rotation angle degree of described major surfaces in the more than 0 ° scope below 360 °, change measured the diffraction peak average intensity of 111} face,

Take described angle of inclination as transverse axis, take diffraction peak intensity as the longitudinal axis, to described { when the diffraction peak average intensity of 111} face is drawn and makes graphic representation, described when connecting described angle of inclination and be 47 °, { { vertical axis intercept of the straight line of the diffraction peak average intensity of 111} face is made as [A] for described when the diffraction peak average intensity of 111} face and described angle of inclination are 53 °, described { when the maximum value of the diffraction peak average intensity of 111} face is made as [B] by described angle of inclination in more than 15 ° 90 ° of following scopes, [A]/[B] >=1/4

And the surfaceness of described major surfaces is, 10 mean roughness Rzjis≤1.2 μ m, arithmetic average roughness Ra≤0.3 μ m.

2. rolled copper foil as claimed in claim 1, is characterized in that, take oxygen free copper or tough pitch copper as principal constituent.

3. rolled copper foil as claimed in claim 1 or 2, is characterized in that, added in silver, boron, titanium, tin at least any.

4. the rolled copper foil as described in any one in claim 1～3, is characterized in that, thickness is below 20 μ m.

5. the rolled copper foil as described in any one in claim 1～4, is characterized in that, for flexibility printed circuit board.