CN103255309A

CN103255309A - Rolled copper foil

Info

Publication number: CN103255309A
Application number: CN2012101890406A
Authority: CN
Inventors: 室贺岳海; 关聪至
Original assignee: Hitachi Cable Ltd
Current assignee: SH Copper Products Co Ltd
Priority date: 2012-02-17
Filing date: 2012-06-08
Publication date: 2013-08-21
Also published as: KR101967714B1; JP5126436B1; KR20130095157A; JP2013170280A

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(113)<=6.0, I{111}<=6.0, and I{133}<=6.0. The half-widths of the diffraction peaks of the crystal faces are FWHM{002}<=0.60, FWHM{022}<=0.50, FWHM{113}<=0.50, FWHM{111}<=0.50, and FWHM{133}<=0.70.

Description

Rolled copper foil

Technical field

The present invention relates to a kind of rolled copper foil, particularly a kind of rolled copper foil that in flexible printing patch panel, uses.

Background technology

Flexible printing patch panel (FPC:Flexible Printed Circuit) because thin, pliability is good, thereby to the degree of freedom height of the installation form of electronics etc.Therefore, the most dogleg section that are used for Collapsible mobile telephone of FPC, digital camera, the first-class moving part of printer, the distribution of the moving part of hard disk drive (HDD:Hard Disk Drive), digital versatile disc (DVD:Digital Versatile Disk), compact disk CD relevant devices such as (CD:Compact Disk) etc.Therefore, to as FPC, its wiring material and the rolled copper foil that uses requires the curved characteristic of the excellence of anti-alternating bending always.

Surface working such as FPC makes through hot rolling, operation such as cold rolling with rolled copper foil, and waits directly by caking agent or by heating and to fit with the basement membrane (base material) of the FPC that is made of resins such as polyimide, the enforcement etching and become distribution.By the state of the recrystallize after the annealing after softening with cold rolling after work hardening after the hard state compare, the curved characteristic of rolled copper foil significantly improves.Therefore can adopt following manufacture method: for example in above-mentioned manufacturing process, use the rolled copper foil after cold rolling, avoiding extending, cutting out rolled copper foil in the distortion such as wrinkle, and it is superimposed on base material, afterwards, hold a concurrent post the recrystallization annealing of rolled copper foil and make rolled copper foil and base material driving fit carry out integrated by heating.

Manufacturing process with above-mentioned FPC is prerequisite, rolled copper foil, its manufacture method about the curved characteristic excellence, carried out various researchs up to now, a lot of reports point out on the surface of rolled copper foil as the cubes orientation { 002} face ({ 200} face) reaches all the more, and then curved characteristic more improves.

Therefore, for example in patent documentation 1, be to carry out final annealing before cold rolling under the condition of 5 μ m ~ 20 μ m in the median size of recrystallize grain, making final cold rolling rolling degree of finish is more than 90%.Thus, obtain recrystallized structure is being carried out under the modified state, by the X-ray diffraction of rolling surface obtain { intensity I of 200} face is with respect to { the intensity I of being obtained by the X-ray diffraction of micropowder copper of 200} face ₀Be I/I ₀＞20 cubes texture.

In addition, for example in patent documentation 2, by improving the flourishing degree of final cubes texture before cold rolling, final cold rolling degree of finish is made as more than 93%, and further implements recrystallization annealing, 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 in the final cold rolling process is made as more than 94%, and the degree of finish of per 1 passage is controlled to be 15% ~ 50%.Thus, after the recrystallization annealing, obtain by the X-ray diffraction pole graph measure the rolling surface obtain { the 111} face is with respect to { orientation degree Δ β is below 10 ° and the ratio of [a] and [b] is the grain orientation state of [a]/[b] 〉=3 in the face of 200} face, described [a] be in the rolling surface as cubes texture { diffraction peak intensity after the stdn of 200} face, described [b] is for { there is the diffraction peak intensity after the crystal region stdn of twin relation in the 200} face.

So in the prior art, by improving total degree of finish of final cold rolling process, after the recrystallization annealing operation, make the cubes texture prosperity of rolled copper foil, thereby realized the raising of curved characteristic.

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

On the other hand, in recent years, along with miniaturization, the slimming of electronics, the situation of bending ground assembling FPC increases gradually in little space.Particularly at the faceplate part of smart mobile phone etc., the FPC that also will form distribution sometimes is bent into 180 ° and assembles, and for rolled copper foil, has improved the requirement of the curved property of folding that allows small-bend radius gradually.

Thus, in order to tackle the requirement according to the curved property of folding of the requirement of high curved characteristiies different, anti-alternating bending such as purposes and anti-small-bend radius, in the past, separately made the rolled copper foil of different qualities for various uses.But there is the problem of profitability difference in this situation efficient that is far from being from the productivity aspect.

The purpose of this invention is to provide after the recrystallization annealing operation, can in high curved characteristic, also have the rolled copper foil of the curved property of good folding.If can realize having concurrently like this rolled copper foil of two specific characters, no matter be that the purposes of the high curved characteristic of attention or the purposes of paying attention to the curved property of folding can both be suitable for then, can significantly improve production efficiency.

According to the 1st mode of the present invention, a kind of rolled copper foil is provided, its be possess major surfaces, have with cold rolling process a plurality of crystal faces of described major surfaces in parallel, final after rolled copper foil before the recrystallization annealing operation, described a plurality of crystal face comprise the 022} face, the 002} face, the 113} face, the 111} face and the 133} face, and will to described major surfaces utilize 2 θ/θ method carry out X-ray diffraction measure and obtain, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _{{ 022}}, I _{{ 002}}, I _{{ 113}}, I _{{ 111}}And I _{{ 133}}The time, I _{{ 113}}≤ 6.0, I _{{ 111}}≤ 6.0 and I _{{ 133}}≤ 6.0,

The wide FWHM that is made as respectively of half value with the diffraction peak of described each crystal face _{{ 022}}, FWHM _{{ 002}}, FWHM _{{ 113}}, FWHM _{{ 111}}And FWHM _{{ 133}}The time, FWHM _{{ 002}}≤ 0.60, FWHM _{{ 022}}≤ 0.50, FWHM _{{ 113}}≤ 0.50, FWHM _{{ 111}}≤ 0.50 and FWHM _{{ 133}}≤ 0.70.

According to the 2nd mode of the present invention, the rolled copper foil of putting down in writing in the 1st mode is provided, will by about have the 022} face, the 002} face, the 113} face, the 111} face and the relative intensity of the standard diffraction peak of described each crystal face of putting down in writing in the JCPDS card of the powder copper of 133} face or the ICDD card obtains, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}The time, I _{{ 113}}/ I _0{113}≤ 0.70, I _{{ 111}}/ I _0{111}≤ 0.12 and I _{{ 133}}/ I _0{133}≤ 1.3.

According to the 3rd mode of the present invention, provide the rolled copper foil of putting down in writing in the 1st or the 2nd mode, wherein I _{{ 002}}〉=7.5.

According to the 4th mode of the present invention, each rolled copper foil of putting down in writing in the 1st ~ the 3rd mode is provided, wherein, will by about have the 022} face, the 002} face, the 113} face, the 111} face and the relative intensity of the standard diffraction peak of described each crystal face of putting down in writing in the JCPDS card of the powder copper of 133} face or the ICDD card obtains, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}The time, I _{{ 002}}/ I _0{002}〉=0.30.

According to the 5th mode of the present invention, each rolled copper foil of putting down in writing in the 1st ~ the 4th mode is provided, be principal constituent with the tough pitch copper of stipulating among the oxygen free copper stipulated among the JIS C1020 or the JIS C1100 wherein.

According to the 6th mode of the present invention, each rolled copper foil of putting down in writing in the 1st ~ the 5th mode is provided, wherein be added with in silver, boron, titanium, the tin at least any.

According to the 7th mode of the present invention, each rolled copper foil of putting down in writing in the 1st ~ the 6th mode is provided, wherein, be that described final cold rolling process more than 90% makes that thickness is below the 20 μ m by total degree of finish.

According to the 8th mode of the present invention, each rolled copper foil of putting down in writing in the 1st ~ the 7th mode is provided, be used for flexible printing patch panel.

According to the present invention, be provided at the rolled copper foil that can have high curved characteristic and the curved property of good folding simultaneously after the recrystallization annealing operation.

Description of drawings

Fig. 1 is the schema of manufacturing process that shows the rolled copper foil of an embodiment of the invention.

Fig. 2 is to use the measurement result of the X-ray diffraction of 2 θ/θ method, (a) be the X ray diffracting spectrum of the rolled copper foil of embodiments of the invention 1, (b) being the X ray diffracting spectrum of the rolled copper foil of comparative example 1, (c) is the X ray diffracting spectrum of the rolled copper foil of comparative example 8.

Fig. 3 is the synoptic diagram of slip bend test device of curved characteristic of measuring the rolled copper foil of embodiments of the invention.

Fig. 4 is the figure of summary of test method of the curved property of folding that shows the rolled copper foil of embodiments of the invention.

Fig. 5 is the antipole point diagram of fine copper shaped metal, (a) for showing the antipole point diagram of the Crystal Rotation direction that tensile deformation causes, (b) for showing the antipole point diagram of the Crystal Rotation direction that compression set causes.

Fig. 6 is the antipole point diagram of the crystal orientation of the rolled copper foil after showing final cold rolling process, before the recrystallization annealing operation.

Nomenclature

10 slip bend test devices

11 sample retaining plates

12 screws

13 vibration reception and registration portions

14 vibration driving bodies

20 barrier sheets

The F coupons

Embodiment

Resulting opinion such as the inventor

As mentioned above, in order to obtain the high rolled copper foil of desired curved characteristic in the FPC purposes, it is more good that the cubes orientation of rolling surface is reached all the more.The inventor etc. also carry out the various experiments be used to the occupation rate increase that makes the cubes orientation always.And, confirmed by experimental result up to now, behind final cold rolling process, exist { 022} looks like the recrystallization annealing operation of fruit by thereafter by modified one-tenth recrystallize, and then becoming { the 002} face, is the cubes orientation.That is, behind final cold rolling process, before the recrystallization annealing operation, preferred { the 022} face becomes main orientation.

On the other hand, even as above-mentioned patent documentation 1 ~ 3, the inventor etc. attempt, make the performance of more cubes texture, in taking the rolled copper foil of polycrystalline structure, as cubes texture { the 002} face can not account for 100% yet.If for example this is the state behind the final cold rolling process; then except as { the 022} face of main orientation; also mix and have a plurality of not controlled { 113} face, { 111} the face, { crystal faces in secondary orientation such as 133} face, and think that these crystal grain with a plurality of crystal faces can produce various influences to every characteristic of rolled copper foil.Therefore, the inventor etc. are conceived to be considered up to now the crystal face in useless secondary orientation always, have inquired in the occupation rate minimizing that does not make main orientation and when keeping high curved characteristic, whether can add new performance by the crystal face in these secondary orientation.

In such research, { the 113} face, { the 111} face, { resolve by the diffraction peak of each crystal face in secondary orientation such as 133} face to comprising for the inventor etc.So conscientiously research found that, carry out various regulations and they are controlled by the state to above-mentioned diffraction peak, thereby give the curved property of good folding as new value added to rolled copper foil, in addition, even { under the situation of the curved characteristic that the control of 022} face and having obtained is stipulated, also can improve curved characteristic more by main orientation.

The present invention is the invention that waits the above-mentioned opinion of finding based on contriver.

An embodiment of the invention

(1) formation of rolled copper foil

The formation of the crystalline structure etc. of the rolled copper foil that relevant an embodiment of the invention are related at first, is described.

The rolled copper foil summary

The related rolled copper foil of present embodiment for example constitutes possesses tabular as the rolling surface of major surfaces.This rolled copper foil is to being that raw-material ingot bar is implemented hot-rolled process described later, cold rolling process etc. and made the rolled copper foil before the recrystallization annealing operation behind specific thickness, the final cold rolling process with fine copper such as oxygen free copper (OFC:Oxygen-Free Copper), tough pitch coppers for example.

The rolled copper foil of present embodiment constitutes the pliability wiring material purposes for for example FPC.That is, the technology of application examples such as above-mentioned patent documentation 3, by total degree of finish be more than 90%, more preferably the final cold rolling process more than 94% constitutes below the thickness 20 μ m.Thereafter, to this rolled copper foil as described above embodiment attempt to possess excellent curved characteristic by recrystallize as holding a concurrent post the recrystallization annealing operation with the bonding process of the base material of FPC.

Becoming raw-material oxygen free copper for example is that the middle purity of stipulating such as JIS C1020, H3100 is the copper material more than 99.96%.Oxygen level can not exclusively be zero, can for example contain the oxygen about several ppm.In addition, tough pitch copper for example is that the purity of regulation among JIS C1100, the H3100 etc. is the copper material more than 99.9%.Under the situation of tough pitch copper, oxygen level for example is about 100ppm ~ 600ppm.Sometimes also in these copper materials trace add the interpolation material of silver regulations such as (Ag) and make the lower concentration copper alloy, thereby make the rolled copper foil of having adjusted every characteristics such as thermotolerance.With regard to the related rolled copper foil of present embodiment, can contain fine copper and lower concentration copper alloy, raw-material copper material, add material the effect of present embodiment is exerted an influence hardly.

The thickness of the processing object thing before the final cold rolling process (sheet material of copper) is made as T _B, the processing object thing behind the final cold rolling process thickness be made as T _AThe time, with total degree of finish (%)=[(T _B-T _A)/T _BTotal degree of finish in the final cold rolling process of] * 100 expression.By being made as total degree of finish more than 90%, more preferably more than 94%, can obtaining having the rolled copper foil of high curved characteristic.

The crystalline structure of rolling surface

The rolling Copper Foil has a plurality of crystal faces that are parallel to rolling surface.Particularly, under the state behind final cold rolling process, before the recrystallization annealing operation, in a plurality of crystal faces, comprise { 022} face, { 002} face, { 113} face, { 111} face and { 133} face.{ the 022} face becomes the main orientation in the rolling surface, and other each crystal face is secondary orientation.

As mentioned above, the state of each the related crystal face proportionlity formula of carrying out various regulation gained by the diffraction peak that each crystal face is measured is controlled.The diffraction peak of each crystal face can be measured to obtain by the X-ray diffraction to the rolling surface of rolled copper foil.

That is, it is 100 ratio that the diffraction peak intensity of above-mentioned 5 crystal faces that will measure by the X-ray diffraction that uses 2 θ/θ method is converted into aggregate value, obtains the diffraction peak intensity ratio of each crystal face.Related diffraction peak intensity than with rolling surface in each crystal face occupation rate about equally.

From the diffraction peak intensity of each crystal face obtain as the representative { conversion formula (A) of the diffraction peak intensity ratio of 022} face is as follows.Here, the diffraction peak intensity ratio with each crystal face is made as I respectively _{{ 022}}, I _{{ 002}}, I _{{ 113}}, I _{{ 111}}And I _{{ 133}}, the diffraction peak intensity of each crystal face is made as I ' respectively _{{ 022}}, I ' _{{ 002}}, I ' _{{ 113}}, I ' _{{ 111}}And I ' _{{ 133}}

Several 1

For the rolled copper foil of present embodiment, the diffraction peak intensity of each crystal face is than there being the relation of for example all setting up with following formula (1) ~ (3).

I _{113}≤6.0···(1)

I _{111}≤6.0···(2)

I _{133}≤6.0···(3)

In addition, on the basis of satisfying above-mentioned (1) ~ (3), further with the wide (half breadth: Full Width at HalfMaximum) be made as FWHM separately of half value of the diffraction peak of above-mentioned each crystal face _{{ 022}}, FWHM _{{ 002}}, FWHM _{{ 113}}, FWHM _{{ 111}}And FWHM _{{ 133}}The time, there is the relation of for example all setting up with following formula (4) ~ (8).

FWHM _{002}≤0.60···(4)

FWHM _{022}≤0.50···(5)

FWHM _{113}≤0.50···(6)

FWHM _{111}≤0.50···(7)

FWHM _{133}≤0.70···(8)

Here, half value is wide to be 1/2 intensity of diffraction peak intensity, i.e. the peak width in 1/2 of diffraction peak height when height.

In addition, the value for the diffraction peak intensity ratio of above-mentioned each crystal face can also be defined as benchmark with the standard diffraction peak intensity ratio of copper.As the standard diffraction peak of copper, can for example exemplify and have { 022} face, { 002} face, { 113} face, { 111} face and the { diffraction peak of the powder copper of 133} face.For example in JCPDS (JCPDS, 40836) or put down in writing the relative intensity of related diffraction peak in ICDD (joint committee, the International Center for Diffraction Data) card Joint Committee for Powder Diffraction Standards) card (card number:.

The relative intensity of the standard diffraction peak of above-mentioned 5 crystal faces can be amounted to that to be converted into aggregate value be 100 ratio, powder copper is obtained the diffraction peak intensity ratio of each crystal face, and with this as benchmark value.

By the relative intensity of the diffraction peak of each crystal face obtain as representative { conversion formula (B) of the diffraction peak intensity ratio of 022} face is as follows.Here, the diffraction peak intensity ratio with each crystal face in the powder copper is made as I respectively _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}, the diffraction peak intensity of each crystal face is made as I respectively ₀' _{{ 022}}, I ₀' _{{ 002}}, I ₀' _{{ 113}}, I ₀' _{{ 111}}And I ₀' _{{ 133}}

Several 2

In the rolled copper foil of present embodiment, except above-mentioned formula (1) ~ (8), the relations that preferred existence is all set up than following formula (9) ~ (11) that are benchmark value with the diffraction peak intensity of each crystal face of above-mentioned powder copper.

I _{113}/I _0{113}≤0.70···(9)

I _{111}/I _0{111}≤0.12···(10)

I _{133}/I _0{133}≤1.3···(11)

In addition, in the rolled copper foil of present embodiment, preferred following formula (12) is set up.

I _{002}≥7.5···(12)

In addition, for above-mentioned the peak intensity of 002} face is than I{002}, and also with powder copper { diffraction peak intensity of 002} face compares I _0{002}Be benchmark value, more preferably can followingly stipulate.

I _{002}/I _0{002}≥0.30···(13)

By last, the rolled copper foil of present embodiment constitutes after the recrystallization annealing operation, has the high curved characteristic of anti-alternating bending, has the curved property of good folding of anti-small-bend radius simultaneously.

The effect of crystalline structure

As mentioned above, before the recrystallization annealing operation the 022} face after the recrystallization annealing operation to the 002} face changes, and before the recrystallization annealing operation { still former state is remaining after the recrystallization annealing operation for the 002} face, thereby improves the curved characteristic of rolled copper foil.In addition { 113} face, { 111} face and { the 133} face is the unwanted crystal face that curved characteristic is not contributed.Therefore, for related crystal face, in above-mentioned formula (1) ~ (3) establishment, when set up preferred above-mentioned formula (9) ~ (11), above-mentioned unwanted crystal face tails off, and is favourable to the raising of curved characteristic.

In addition, discoveries such as the inventor for related crystal face, have relations that above-mentioned formula (1) ~ (3) all set up, when preferably having concerning that above-mentioned formula (9) ~ (11) all set up, can bring into play the curved property of good folding after the recrystallization annealing operation.That is, if { 113} face, { 111} face and { the 133} face is all low than requirement ratio, the then curved property raising of folding in each secondary orientation.

On the other hand, even the value of each crystal face that has suppressed secondary orientation is to satisfy above-mentioned formula (1) ~ (3), formula (9) ~ (11), as mentioned above, also can be owing to rolled copper foil is that polycrystal certainly exists secondary orientation.Therefore, the inventor etc. also are conceived to the proper alignment state of each crystal face before and after the recrystallize, stipulate related proper alignment state by above-mentioned formula (4) ~ (8).

That is, by with become behind the recrystallize before the recrystallize of 002} face do not change behind 022} face and the recrystallize yet, as { { the wide FWHM of the half value of 002} face that the recrystallize of 002} face is preceding _{{ 022}}And FWHM _{{ 002}}The upper limit suc as formula (4) and determine (5), behind the recrystallize { the interval unanimity between the crystal face of 002} face becomes the state of proper alignment.Therefore, can make the copper atom ordered state behind the recrystallize consistent well, thereby can obtain good curved characteristic.

In addition, { 113} face, { the 111} face and { the 133} face can hinder { the proper alignment of 002} face behind the recrystallize that mix to exist in the crystal.Therefore, by the wide FWHM of the half value that makes these each crystal faces _{{ 113}}, FWHM _{{ 111}}And FWHM _{{ 133}}Satisfy above-mentioned formula (6) ~ (8), and make these each crystal faces reach the state of proper alignment under the state before recrystallize, thereby be difficult for { the proper alignment of 002} face behind the obstruction recrystallize.

Like this, the peak width of diffraction peak is represented the deviation at the interval of the crystal face corresponding with this diffraction peak (lattice plane).This can describe by bragg's formula 2dsin θ=n λ.Here, n is positive integer, and λ is wavelength, and d is that interval, the θ of lattice plane is grazing angle (input angle).Diffraction peak exists width to refer to, self there are width in 2 θ and then grazing angle θ, are deviation.At this moment, according to bragg's formula, positive integer n is all fixing with the wavelength X as the wavelength of the pipe ball of X-ray generator.Therefore, when there is width in grazing angle θ, fix in order to make 2dsin θ, also must there be width in the interval d of lattice plane.

So, even the copper crystal of identical crystal face (crystal orientation), if if grazing angle θ is different, then the interval d of lattice plane is also different.Therefore, the half value of diffraction peak is wide more narrow, and then the deviation of the interval d of this lattice plane is more little, and the ordered state of copper atom is more good, that is, and and the copper atom proper alignment.On the other hand, the half value of diffraction peak is wide more wide, and then the deviation of the interval d of this lattice plane is more big.

Therefore, except will { the 113} face, { the 111} face, { ratio of the crystal face in secondary orientation such as 133} face suppresses by making above-mentioned 5 crystal face proper alignment, also can improve curved characteristic more for low under the situation that obtains high curved characteristic.

In addition, except above-mentioned, the inventor etc. also find, in the rolled copper foil behind final cold rolling process, before the recrystallization annealing operation, exist for the 002} face, and have promotion because of the recrystallization annealing operation cause from { 022} is towards { the effect that the 002} face changes.Therefore, preferred above-mentioned formula (12) is set up, and more preferably above-mentioned formula (13) is set up, thereby can obtain morely after the recrystallization annealing operation that { the 002} face can obtain good bent characteristic more.

By last, the diffraction peak intensity of each crystal face than, be that the balance of diffraction peak intensity can greatly influence curved characteristic, the bending generation of rolled copper foil.The balance of the diffraction peak intensity of each related crystal face as described later main during by final cold rolling process stress under compression and the stress equilibrium of tensile stress decide.

(2) manufacture method of rolled copper foil

Then, use Fig. 1 that the manufacture method of the rolled copper foil of an embodiment of the invention is described.Fig. 1 is the schema of the manufacturing process of the rolled copper foil of demonstration present embodiment.

The preparatory process S10 of ingot bar

As shown in Figure 1, at first fine copper such as oxygen free copper (OFC:Oxygen-Free Copper), tough pitch copper are cast as starting material, prepared ingot bar (ingot casting).Ingot bar for example forms has the tabular of specific thickness, Rack.Can form the lower concentration copper alloy that in becoming fine copper such as raw-material oxygen free copper, tough pitch copper, has added the interpolation material of regulation for every characteristic of adjusting rolled copper foil.

By adding in the adjustable above-mentioned every characteristic of material, thermotolerance is for example arranged.As mentioned above, for the FPC rolled copper foil, the bonding process that the recrystallization annealing operation that is used for obtaining high curved characteristic is for example held a concurrent post with the base material of FPC carries out.Heating temperature during applying for example waits to set the wide ranges of temperature condition and varied according to the solidification value of the caking agent of the solidification value of the base material of being made up of resin etc. of FPC, use.For the softening temperature that makes rolled copper foil and the Heating temperature of so setting adapt, add the stable on heating interpolation material that to adjust rolled copper foil sometimes.

As the ingot bar that uses in the present embodiment, following table 1 illustration does not have the ingot bar that adds material, the ingot bar that has added the interpolation material of several types.

Table 1

In addition, as the interpolation material shown in the above-mentioned table 1, other adds material, in the typical example of the interpolation material that thermotolerance is risen or descend, the example that adds any or multiple element in for example boron about 10ppm ~ 500ppm (B), niobium (Nb), titanium (Ti), nickel (Ni), zirconium (Zr), vanadium (V), manganese (Mn), hafnium (Hf), tantalum (Ta) and the calcium (Ca) is arranged.Perhaps, have and add Ag as the 1st adding element, adding any or multiple element in the above-mentioned element as the 2nd example that adds element.In addition, also can add chromium (Cr), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), Cd (cadmium), indium (In), tin (Sn), antimony (Sb), gold (Au) etc. by trace.

Need to prove that the composition of ingot bar also can remain unchanged substantially in through the rolled copper foil behind the final cold rolling process S40 described later, in ingot bar, add when adding material that ingot bar becomes identical substantially interpolation material concentration with rolled copper foil.

In addition, the temperature condition among the annealing operation S32 described later suits to change according to the thermotolerance that copper material, interpolation material bring.But, above-mentioned copper material, add material, the change etc. of the temperature condition of corresponding annealing operation S32 is for the almost not influence of effect of present embodiment therewith.

Hot-rolled process S20

Then, ready ingot bar is implemented hot rolling, make the sheet material of the thickness of slab thinner than the specific thickness after the casting.

Operation S30 repeatedly

Then, implement the cold rolling process S31 of stipulated number and the S30 of operation repeatedly of annealing operation S32 repeatedly.That is, by above-mentioned sheet material enforcement anneal after the work hardening is come sheet material is annealed to implementing cold rolling, thereby make work hardening obtain relaxing.By carrying out this operation of stipulated number repeatedly, can be called as the copper bar of " blank ".Copper material has been added when adjusting stable on heating interpolation material etc., according to the suit temperature condition of change anneal of the thermotolerance of copper material.

Need to prove, in operation S30 repeatedly, the annealing operation S32 in the repetitive process is called " process annealing operation ".In addition, with repeatedly last, be that the annealing operation S32 that carries out before the final cold rolling process S40 described later is called " final annealing operation " or " blank anneal operation ".

By the number of occurrence of above-mentioned process annealing operation, can control the interval of the lattice plane of each crystal behind the final cold rolling process S40 of aftermentioned, namely the half value of the diffraction peak of each crystal face is wide.In order to make related half value wide in the prescribed value, the number of occurrence that preferably makes the process annealing operation is more than 3 times.

In the blank anneal operation of carrying out at last repeatedly, above-mentioned copper bar (blank) is implemented blank anneal handle, obtain the blank of annealing.In the blank anneal operation, also according to the thermotolerance of the copper material changing temperature condition that suits.At this moment, the blank anneal operation is preferably at the temperature condition that can fully relax the caused processing strain of above-mentioned each operation, for example handle under the equal substantially temperature condition with Full Annealing and implement.

Final cold rolling process S40

Then, implement final cold rolling process S40.Final cold rolling be also referred to as refining cold rolling, refining cold rolling through repeatedly the annealing blank being implemented to become.At this moment, the technology of application examples such as patent documentation 3 in the present embodiment, with total degree of finish be made as more than 90%, more preferably more than 94%, to obtain to have the rolled copper foil of high curved characteristic.Thus, after the recrystallization annealing operation, become the rolled copper foil that is easy to obtain the higher rate of curving.

In addition, whenever repeat repeatedly cold rollingly, the annealing blank can attenuation, and corresponding to this, advantageous applications is the technology of patent documentation 3 for example, reduces the degree of finish of per 1 time (1 passage) at leisure gradually., imitate the example of above-mentioned total degree of finish here, the thickness of the processing object thing before n passage rolling is made as T _Bn, the processing object thing after rolling thickness be made as T _AnThe time, with degree of finish (the %)=[(T of per 1 passage _Bn-T _An)/T _BnThe degree of finish of per 1 passage of] * 100 expression.

Rollingly add man-hour, processing object things such as annealing blank are by for example being drawn into the gap between 1 pair roller respect to one another, and are drawn out from opposition side, thereby reduce thickness.The inlet side of the speed of processing object thing before being drawn into roller is slower than the velocity of rotation of roller, and the outlet side after pulling out from roller is faster than the velocity of rotation of roller.Therefore, the processing object thing is applied stress under compression at inlet side, apply tensile stress at outlet side.For the processing object thing is processed thinly, must make stress under compression＞tensile stress.By adjusting the degree of finish of per 1 passage, can be the ratio that stress component (compression composition and stretching composition) is separately adjusted on prerequisite ground with stress under compression＞tensile stress.Thus, as mentioned above, the stress equilibrium of stress under compression and tensile stress changes, and can adjust the ratio of the crystal face in secondary orientation.

In addition, in final cold rolling process S40, preferably repeat repeatedly cold rollingly with every, below the position of Shuo Ming the neutrality point mode that will move to the outlet side of roller is controlled.That is, as mentioned above, becoming with a certain position of speed between inlet side and outlet side of outlet side magnitude relationship processing object thing conversely at inlet side with respect to the velocity of rotation of roller equates with the velocity of rotation of roller.The position that both speed equates with this is called neutral point, at neutrality point to processing object thing institute applied pressure maximum.

The position of neutral point can be controlled by the combination of adjusting the place ahead tension force, rear tension force, roll speed (velocity of rotation of roller), roller footpath, degree of finish, rolling load etc.That is, by controlling the position of neutral point, also can adjust the ratio of stress under compression and tensile stress, can adjust the ratio of the crystal face in secondary orientation.

As mentioned above, the balance of the diffraction peak intensity of each crystal face can greatly influence curved characteristic, the bending generation of rolled copper foil, putting down of the diffraction peak intensity of each related crystal face, the stress under compression during mainly by final cold rolling process and the stress equilibrium of tensile stress decide.

Particularly, final cold rolling process S40 etc. are rolling to add man-hour, the stress of the copper crystal in the copper material during owing to the rolling process phenomenon that rotates, and by some paths to { 022} face variation.Stress under compression is more big, then more is easy to via { the 002} face, { 113} is towards { the 022} face changes, and tensile stress is more big, then more is easy to via { the 111} face, { 133} is towards { the 022} face changes.

Like this, by the size control of carrying out the degree of finish in each passage, the position control of neutral point etc., implement final cold rolling process S40 simultaneously, can be met the rolled copper foil of above-mentioned formula (1) ~ (13).Therefore, can obtain the recrystallization annealing operation after, have the high curved characteristic of anti-alternating bending, have the rolled copper foil of the curved property of good folding of anti-small-bend radius simultaneously.

Surface treatment procedure S50

To implement the surface treatment of regulation through the copper bar of above operation.By on can make the rolled copper foil of present embodiment.

(3) manufacture method of flexible printing patch panel

Below, the manufacture method of the flexible printing patch panel (FPC) that uses the related rolled copper foil of one embodiment of the present invention is described.

Recrystallization annealing operation (CCL operation)

At first, the rolled copper foil of present embodiment is cut into the size of regulation, for example the base material of the FPC that constitutes with resin by polyimide etc. is fitted and is formed CCL (copper clad laminate, Copper Clad Laminate).At this moment, can use by caking agent and fit to form the method for 3 layers of material CCL and directly do not fit to form in the method for 2 layers of material CCL any by caking agent.When using caking agent, by heat treated caking agent is solidified, and make rolled copper foil and base material driving fit and carry out integrated.When not using caking agent, make rolled copper foil and the direct driving fit of base material by heating, pressurization.Heating temperature, time can for example can be made as the temperature below 400 ℃ more than 150 ℃ according to the suitable selections such as solidification value of caking agent, base material, more than 1 minute below 120 minutes.

As mentioned above, adjusted the thermotolerance of rolled copper foil according to the Heating temperature of this moment.Therefore, rolled copper foil softens and recrystallize by above-mentioned heating.That is, hold a concurrent post recrystallization annealing operation to rolled copper foil to the CCL operation of base material applying rolled copper foil.By rolled copper foil is implemented recrystallization annealing operation, the rolled copper foil that can obtain having recrystallized structure.That is, become the rolled copper foil that has high curved characteristic, has the curved property of good folding simultaneously.

In addition, hold a concurrent post the recrystallization annealing operation by the CCL operation thus, thereby in the operation before rolled copper foil is fitted to base material, can under the state after the work hardening behind the cold rolling process, handle rolled copper foil, and can be difficult for producing the distortion of elongation when rolled copper foil fitted to base material, wrinkle, bending etc.

In addition, each crystal face in secondary orientation changes before and after the recrystallization annealing operation hardly.Therefore in order to obtain the curved property of high curved characteristic and folding, as long as the above-mentioned relation formula is satisfied in the control that the rolled copper foil behind the final cold rolling process, before the recrystallization annealing operation is carried out secondary orientation.

The surface working operation

Then, the rolled copper foil that fits on the base material is implemented the surface working operation.In the surface working operation; carry out distribution and form operation, surface treatment procedure and protective membrane formation operation; it is rolled copper foil for example to be used method such as etching form copper wiring etc. that described distribution forms operation; described surface treatment procedure is to implement surface treatment such as plating processing for the connection reliability that improves copper wiring and other electronic unit, and it is the protective membrane that forms solder resist etc. in order to protect copper wiring etc. in the mode of the part on the covering copper distribution that described protective membrane forms operation.

By on can make the FPC of the rolled copper foil that uses present embodiment.

Other embodiment of the present invention

More than, specifically understand relevant embodiments of the present invention, still, the present invention is not limited to above-mentioned embodiment, can carry out various changes in the scope that does not break away from its main idea.

For example, in the above-described embodiment, mainly use Ag as the stable on heating interpolation material of adjusting rolled copper foil, be not limited to the material enumerated in Ag, the above-mentioned typical example etc. but add material.In addition, be not limited to thermotolerance by adding the adjustable every characteristic of material, the every characteristic that can adjust as required suits to select the interpolation material.

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

In addition, in the above-described embodiment, rolled copper foil is used for the FPC purposes, but the purposes of rolled copper foil is not limited to this, needing can be used for the purposes of high curved characteristic and the curved property of folding.For the thickness of rolled copper foil, according to the various uses headed by the FPC purposes, also can surpass 20 μ m etc.

In addition, in order to bring into play effect of the present invention, the above-mentioned operation of enumerating might not be all necessary.The various conditions that above-mentioned embodiment, embodiment described later enumerate are illustration also, can suit to change.

Embodiment

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

(1) rolled copper foil of use oxygen free copper

At first, the embodiment 1 ~ 7 of oxygen free copper and the rolled copper foil of comparative example 1 ~ 14 are used in following making, and carry out various evaluations respectively.

The making of rolled copper foil

Use and added the oxygen free copper of aimed concn as the Ag of 150ppm, with step and the method same with above-mentioned embodiment, make the rolled copper foil of embodiment 1 ~ 7 and comparative example 1 ~ 14.But, for comparative example 1 ~ 14, comprise processing that departs from formation etc.

Particularly, prepare the Ag of fusion specified amount in oxygen free copper and the thickness cast is that 150mm, width are the ingot bar of 500mm.Following table 2 shows the analytical value of Ag concentration that analyze by high-frequency inductor coupled plasma (ICP:Inductively Coupled Plasma) Emission Spectrophotometer method, in the ingot bar.

Table 2

As shown in table 2, with respect to the 150ppm of aimed concn, analytical value is 136ppm ~ 165ppm, all is suppressed to deviation interior about 150ppm ± 15ppm (10%).Except Ag originally contains about several ppm ~ tens ppm as inevitable impurity in as main raw-material oxygen free copper sometimes, a variety of causes such as deviation during owing to cast billets, deviation interior about ± 15ppm is common in metal material field.

Then, with step and the method same with above-mentioned embodiment, after in hot-rolled process, obtaining sheet material that thickness is 8mm, implement cold rolling process repeatedly and under 700 ℃ ~ 800 ℃ temperature, keep about 2 minutes process annealing operation, thereby make copper bar (blank).At this moment, the number of occurrence that makes the process annealing operation is more than 3 times in embodiment 1 ~ 7, is below 2 times in comparative example 1 ~ 14, thereby makes the wide generation difference of half value of the diffraction peak of each crystal face.

Then, by under about 750 ℃ temperature, keeping about 1 minute blank anneal operation to obtain the blank of annealing.Here, temperature condition of each annealing operation etc. is fit to contain the thermotolerance of anaerobic copper material of the Ag of 136ppm ~ 165ppm.Need to prove that for forming identical copper material, adopting different temperature condition in each annealing operation is that thermotolerance can change, and when copper material is thin, can reduce temperature owing to the thickness according to copper material.

At last, to carry out final cold rolling process with same step and the method for above-mentioned embodiment, obtain the related rolled copper foil of embodiment 1 ~ 7 and comparative example 1 ~ 14.Following table 3 shows the condition of final cold rolling process.In the table 3, last table is the final cold rolling process condition of embodiment 1 ~ 7, and following table is the final cold rolling process condition of comparative example 1 ~ 14.

Table 3

The final cold rolling process condition of embodiment 1 ~ 7

The final cold rolling process condition of comparative example 1 ~ 14

* the length from the outlet side end to neutrality point of the contact surface of roller and processing object thing

As shown in table 3, according to from the epimere of each table to the attenuation in turn of hypomere thickness of slab, conversion condition as right hurdle is carried out finally cold rolling.That is, making thickness is that the following degree of finish cold rolling processing, per 1 passage of 240 μ m changes with neutral position of putting.On the border of separately thickness range, when rolling pass strides across this border, the rolling condition below after striding across the border, being suitable for.For example, in the condition at the epimere of embodiment 1 ~ 7 of table, be 25% and begin to carry out when cold rolling from thickness 240 μ m with the degree of finish of 1 passage, the thickness of copper bar becomes 180 μ m in the 1 initial passage.At this moment, even in following 1 passage, become the less than 160 μ m of the thickness range of the condition that departs from epimere, still keep degree of finish and be 18% with on carry out cold rollingly, the 2nd section condition of last table is suitable after the rolling pass of this time.Need to prove, in the condition at comparative example 1 ~ 14 of following table, in the scope of thickness 240 μ m ~ 200 μ m, do not specify cold rolling condition.

The position (mm) of the neutrality point shown in the right hurdle is represented with roller and as the length from the outlet side end to neutrality point of the contact surface of the annealing blank of processing object thing.Described neutral point be for the parsing peak intensity that obtains stipulating by employed roller mill in the present embodiment than and the wide and value of special adjustment of half value.

In addition, in order to obtain excellent curved characteristic, in embodiment 1 ~ 7 and comparative example 1 ~ 14 whole, impose a condition so that the total degree of finish in final cold rolling process is 95%.By the last making thickness embodiment 1 ~ 7 that is 12 μ m and the rolled copper foil of comparative example 1 ~ 14.

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

Utilize the X-ray diffraction of 2 θ/θ method to measure

At first, the rolled copper foil to embodiment 1 ~ 7 and comparative example 1 ~ 14 utilizes the X-ray diffraction of 2 θ/θ method to measure.Related mensuration is used the X-ray diffraction device (model: Ultima IV), carry out of Co., Ltd. Neo-Confucianism's system under the condition shown in the following table 4.As representative, the X ray diffracting spectrum of Fig. 2 (a) expression embodiment 1, Fig. 2 (b), (c) expression comparative example 1,8 X ray diffracting spectrum.

Table 4

Then, { 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 that will measure by 2 θ/θ method.In following table 5, show the rolled copper foil for embodiment 1 ~ 7 and comparative example 1 ~ 14, compare I by the diffraction peak intensity of above-mentioned each crystal face of obtaining _{{ 022}}, I _{{ 002}}, I _{{ 113}}, I _{{ 111}}And I _{{ 133}}Value.

Table 5

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

In addition, it is wide to obtain the half value of diffraction peak of each crystal face by the X ray diffracting spectrum of embodiment 1 ~ 7 and comparative example 1 ~ 14.In the following table 6, show the related wide FWHM of half value _{{ 022}}, FWHM _{{ 002}}, FWHM _{{ 113}}, FWHM _{{ 111}}And FWHM _{{ 133}}Value.

Table 6

In addition, for powder copper, according to card number: the record of 40836 JCPDS card, obtain the relative intensity with the standard diffraction peak of above-mentioned same each crystal face.That is, obtain so that { the 111} face is 100 each crystal face { 022} face, { 002} face, { 113} face, { 133} face relative intensity 20,46,17,9 separately.

The relative intensity of described 5 diffraction peaks amounted to be converted into aggregate value be 100 ratio, powder copper is obtained the diffraction peak intensity ratio of each crystal face.

Further, the diffraction peak intensity ratio of the diffraction peak intensity ratio of the rolled copper foil shown in the use table 5 and above-mentioned powder copper is obtained the numerical value that above-mentioned formula (9) ~ (11) reach (13).The diffraction peak intensity that shows each crystal face of powder copper in the epimere of following table 6 compares I _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}Value.In addition, in hypomere, show the numerical value that is reached (13) by above-mentioned above-mentioned formula (9) ~ (11 of obtaining).

Table 7

*I _0{022}+I _0{002}+I _0{113}+I _0{111}+I _0{133}＝100

As mentioned above, in present embodiment and the comparative example, the number of occurrence of the process annealing operation in the operation, the degree of finish of per 1 passage in the final cold rolling process and the position of neutral point have been changed repeatedly.Thus, cold rollingly add man-hour, the compression composition that the processing object thing is applied changes with the ratio of the stress component of stretching composition.Its result, the ratio vary of each crystal face, the diffraction peak intensity of each crystal face shown in the table 5 is wideer than the half value shown in, the table 6, formula (9) ~ (11) shown in the table 7 and the numerical value of (13) also change.

In addition, shown in table 5 ~ 7, in the combination of each condition of embodiment 1 ~ 7, each value of formula (1) ~ (13) is all in above-mentioned specialized range.

On the other hand, in the combination of each condition of comparative example 1 ~ 7, for formula (1) ~ (3) and (12) and formula (9) ~ (11) and (13), all satisfy prescribed value, but in arbitrary rolled copper foil, the one or more values in each value of formula (4) ~ (8) are outside above-mentioned specialized range.In addition, in the combination of each condition of comparative example 8 ~ 14, in arbitrary rolled copper foil, a plurality of values in each value of formula (1) ~ (13) are outside above-mentioned specialized range.In table 5 ~ 7, show the value that departs from above-mentioned specialized range with the thick word table of being with underscore.

As mentioned above, for the rolled copper foil after the recrystallization annealing operation, in order when obtaining the curved property of good folding, further to improve script with regard to high curved characteristic, on the basis of satisfying above-mentioned formula (1) ~ (3) at least, need further satisfy above-mentioned formula (4) ~ (8).Before reference, for above-mentioned formula (1) ~ (8), whether embodiment 1 ~ 7 and comparative example 1 ~ 14 are adapted at showing in the following table 8.In the table 8, suitable above-mentioned formula (1) ~ (8) person is designated as zero (in the specialized range), the person of being not suitable for is designated as * (specialized range is outer).

Table 8

Zero: in the specialized range *: outside the specialized range

Crystal face

Formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (5)

Formula (6)

Formula (7)

Formula (8)

Embodiment-1

○

Embodiment-2

○

Embodiment-3

○

Embodiment-4

○

Embodiment-5

○

Embodiment-6

○

Embodiment-7

○

Comparative example-1

○

×

○

Comparative example-2

○

×

○

×

○

Comparative example-3

○

×

○

Comparative example-4

○

×

Comparative example-5

○

×

○

Comparative example-6

○

×

○

×

○

Comparative example-7

○

×

○

Comparative example-8

○

×

○

×

○

Comparative example-9

○

×

○

Comparative example-10

○

×

○

×

Comparative example-11

×

○

×

○

Comparative example-12

×

○

×

○

×

Comparative example-13

○

×

○

×

○

Comparative example-14

○

×

○

×

The flexible life test

Then, in order to study the curved characteristic of each rolled copper foil, measure the flexible life test of the alternating bending number of times (number of bends) of each rolled copper foil till fracture.The FPC high speed bend test machine (model: SEK-31B2S), carry out according to IPC (U.S.'s printed wiring industry meeting) standard of Shinetsu Eng Co., Ltd. (エ of SHIN-ETSU HANTOTAI Application ジニアリ Application ゲ Co., Ltd.) system is used in related test.Fig. 3 shows the synoptic diagram of the general slip bend test device 10 also comprise above-mentioned FPC high speed bend test machine etc.

At first, imitate above-mentioned recrystallization annealing operation, it is that 12.5mm, length are that the thickness of 220mm gained is that the coupons F of 12 μ m implements 300 ℃, 60 minutes recrystallization annealing that the rolled copper foil with embodiment 1～7 and comparative example 1～14 is cut into width.In the CCL operation that related condition has been imitated at flexible printing patch panel, during with the base material driving fit, an example of the actual heat that bears of rolled copper foil.

Then, as shown in Figure 3, the coupons F of rolled copper foil is fixed on the sample retaining plate 11 of slip bend test device 10 with screw 12.Then, coupons F contact with vibration reception and registration portion 13 and paste, by vibration driving body 14 vibration reception and registration portion 13 is vibrated at above-below direction, vibration is conveyed to coupons F, implement flexible life and test.As the condition determination of flexible life, radius of curvature R is made as 1.5mm, stroke S are made as 10mm, the amplitude number is made as 25Hz.Under this condition, measure each 5 of the coupons F that cut from each rolled copper foil, relatively up to the mean value of the number of bends that fracture takes place.Following table 9 display result.

Table 9

As mentioned above, each rolled copper foil is 95% final cold rolling process through making total degree of finish, and is as shown in table 9, even comparative example 1 ~ 14 has also obtained flexible life, has been that number of bends is the high curved characteristic more than 1,000,000 times.

On the other hand, among the embodiment 1 ~ 7, through the final cold rolling process of total degree of finish 95%, making above-mentioned formula (the 1) ~ value of (13) all in specialized range simultaneously, is better curved characteristic more than 2,000,000 times thereby obtained number of bends.This is the value that surpasses the high level of the comparative example 1 ~ 14 that had high curved characteristic originally.

The evaluation of the curved property of folding

Then, study the curved property of folding of each rolled copper foil.In the general touchstone for the curved property of folding, also there is not the stdn about middle 180 ° of bendings that require such as for example FPC purposes.Therefore, carry out folding test by method shown in Figure 4, measure each rolled copper foil until the bending times of breaking.

That is, at first, to the rolled copper foil of embodiment 1 ~ 7 and comparative example 1 ~ 14 is cut out the coupons F of wide 15mm, long 100mm gained with respect to rolling direction, implement 300 ℃, 60 minutes recrystallization annealing.Then, as shown in Figure 4, with 180 ° of coupons F bendings, with the barrier sheet 20 that sandwiches thickness 0.15mm, use metal microstructure sem observation dogleg section in this state, confirm to have crack-free.If do not break, then rolled copper foil is returned to original extended configuration from the bending state.Be 1 circulation with it, for each 5 of the coupons F that cuts out from each rolled copper foil, carry out the observation of dogleg section in per 1 circulation, circulate repeatedly until breaking the mensuration bending times.Display result in the following table 10.

Table 10

As shown in table 10, among embodiment 1 ~ 7 and comparative example 1 ~ 7 arbitrary, bending times all is more than 50 times, has all obtained the curved property of good folding.On the other hand, among comparative example 8 ~ 14 arbitrary, bending times is less than 50 times all, does not all obtain the curved property of sufficient folding.The results are summarized in the following table 11 more than inciting somebody to action.

Table 11

As shown in table 11, arbitrary rolled copper foil all is 95% final cold rolling process through total degree of finish, thereby has obtained the curved characteristic of regulation.Wherein, have only and satisfy above-mentioned formula (4) ~ (8) and the embodiment 1 ~ 7 that the proper alignment state of each crystal face has also taken in is shown better curved characteristic.

(2) rolled copper foil of use tough pitch copper

Then, use and added the tough pitch copper of aimed concn as the Ag of 200ppm, with step and the method same with the above embodiments, make thickness and be the embodiment 8 of 12 μ m and comparative example 15,16 related rolled copper foils.But, for comparative example 15,16, comprise processing that departs from formation etc.

Ag concentration in embodiment 8 and comparative example 15,16 the ingot bar is respectively 190ppm, 195ppm and 185ppm for by the resulting analytical value of IPC Emission Spectrophotometer method.In addition, according to the thermotolerance of the tough copper material of the Ag that contains related concentration, in process annealing operation and blank anneal operation, use and above-mentioned different condition.Particularly, in the process annealing operation, approximately kept 2 minutes 650 ℃ ~ 750 ℃ temperature, in the blank anneal operation, approximately kept 1 minute in about 700 ℃ temperature.

For the embodiment 8 that makes as described above and comparative example 15,16 rolled copper foil, with method and the step same with the above embodiments, utilize the X-ray diffraction of 2 θ/θ method to measure, obtain above-mentioned formula (1) ~ (8).Its result, for the rolled copper foil of embodiment 8, the pass of the diffraction peak intensity of each crystal face ties up in the various specialized range.On the other hand, for the rolled copper foil of comparative example 15, though satisfy formula (1) ~ (3), the half value that has departed from the regulation diffraction peak is wide and help formula (4), (5) of the raising of curved characteristic, the specialized range of (7).In addition, for the rolled copper foil of comparative example 16, departed from the specialized range of each formula (2) of helping the curved property of folding and curved characteristic, (3), (5), (7).

In addition, for embodiment 8 and comparative example 15,16 rolled copper foil, carry out the flexible life test by method and step that above-described embodiment is same.Its result, each rolled copper foil is through the final cold rolling process of total degree of finish 95%, even comparative example 15,16 has also obtained so good curved characteristic more than 1,000,000 times respectively 1,767,000 time, 1,790,000 time.On the other hand, for above-mentioned formula (1) ~ (8) embodiment in specialized range 8 all, obtained the value of 2,125,000 so better curved characteristic of demonstration more than 2,000,000 times.

In addition, for embodiment 8 and comparative example 15,16 rolled copper foil, by carrying out folding test with same method and the step of above-described embodiment.Its result, for embodiment 8 and comparative example 15, bending times is respectively done for oneself 65 times, 67 times, and is better, relative therewith, for comparative example 16, is 38 times poor outcome.

As known from the above, if each crystal face is in specialized range, even then for being main raw-material rolled copper foil with the tough pitch copper, also can obtain good bending, and seek the further raising of curved characteristic.

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

Then, use added aimed concn as the Ag of 120ppm and aimed concn as the titanium (Ti) of 40ppm as the oxygen free copper that adds material, to make embodiment 9 that thickness is 12 μ m and comparative example 17,18 rolled copper foil with the same step of above-described embodiment and method.But, for comparative example 17,18, comprise processing that departs from formation etc.

Ag concentration in embodiment 9 and comparative example 17,18 the ingot bar is respectively 117ppm, 121ppm and 118ppm for by the resulting analytical value of IPC Emission Spectrophotometer method.In addition, Ti concentration is respectively 38ppm, 38ppm and 40ppm.Being ± deviation in about 10%, is common in metal material field.

In addition, according to the thermotolerance of the anaerobic copper material of the Ag that contains above-mentioned concentration and Ti, in process annealing operation and blank anneal operation, adopt and above-mentioned different condition.Particularly, in the process annealing operation, kept about 2 minutes for 650 ℃ ~ 750 ℃ in temperature, in the blank anneal operation, kept about 1 minute in about 700 ℃ temperature.

For the embodiment 9 that makes as mentioned above and comparative example 17,18 rolled copper foil, measure with the X-ray diffraction that utilizes 2 θ/θ method with the same method of above-described embodiment and step, obtain above-mentioned formula (1) ~ (8).Its result, for the rolled copper foil of embodiment 9, the pass of the diffraction peak intensity of each crystal face ties up in the specialized range of formula (1) ~ (8).On the other hand.For the rolled copper foil of comparative example 17, though satisfy formula (1) ~ (3), the half value that has departed from the regulation diffraction peak is wide and help the specialized range of formula (4) that curved characteristic improves, (5), (6).In addition, for the rolled copper foil of comparative example 18, the both sides' that help the curved property of folding and curved characteristic formula (2), (3), (7), the specialized range of (8) have been departed from.

In addition, for embodiment 9 and comparative example 17,18 rolled copper foil, by carrying out the flexible life test with same method and the step of above-described embodiment.Its result, each rolled copper foil is through the final cold rolling process of total degree of finish 95%, even comparative example 17,18 also obtains so good curved characteristic more than 1,000,000 times respectively 1,781,000 time, 1,756,000 time.On the other hand, above-mentioned formula (1) ~ (8) all among the embodiment in specialized range 9, have obtained the value of 2,139,000 so better curved characteristic of demonstration more than 2,000,000 times.

In addition, for embodiment 9 and comparative example 17,18 rolled copper foil, by carrying out folding test with same method and the step of above-described embodiment.Its result, for embodiment 9 and comparative example 17, bending times is respectively 68 times, 67 times, and is better, relative therewith, for comparative example 18, is 33 times poor outcome.

As known from the above, if each crystal face is in specialized range, even then for having added Ag and the so different rolled copper foils that add materials of Ti, also can obtain good curved characteristic and bending.

The inventor's etc. investigation

For coming to give the principle of the curved property of folding and for the controlling mechanism of the crystal face in secondary orientation in the manufacturing process of above-mentioned rolled copper foil to rolled copper foil by the crystal face of controlling secondary orientation as mentioned above, the below explanation inventor's etc. investigation.

(1) about giving the principle of the curved property of folding

Opinion, the opinion of Metallkunde and experiment experience up to now that the inventor etc. learn according to crystal orientation for the principle that obtains the curved property of folding by the crystal face of controlling secondary orientation, have carried out following investigation.

According to the inventor etc., think that not changing of the variation of the curved property of resulting folding and the main orientation of recrystallization annealing operation front and back among the present invention and secondary orientation is relevant.As mentioned above, in the recrystallization annealing operation, as main orientation { the 022} face becomes { 002} face behind recrystallize.On the other hand, as { 002} face, { 113} face, { the 111} face and { the 133} face does not substantially change behind recrystallize yet, thinks that { angulation is related to folding and bends property between the 002} face for the crystal face in the main orientation behind these secondary orientation and the recrystallize in secondary orientation.

Recrystallize { 002} face ∠ { 113} face: 25.2 °

Recrystallize { 002} face ∠ { 111} face: 54.7 °

Recrystallize { 002} face ∠ { 133} face: 46.5 °

That is, { the 113} face is with { the 002} face is 25.2 ° angular relation, and { the 111} face is with { 002} is 54.7 ° angular relation, and { the 133} face is with { the 002} face is 46.5 ° angular relation.Thus, with recrystallize after { 002} face angulation is all bigger.

During the state of the application's rolled copper foil behind final cold rolling process, before the recrystallization annealing, above-mentioned formula (1) ~ (3) and more preferably formula (9) ~ (11) in specialized range, mean, the ratio of these 3 crystal faces all is suppressed to lower, even after recrystallize, with { crystal face that 002} face angulation is bigger is also few.Especially be the numerical value of regulation when following when the ratio of the bigger crystal face of these angles, mean to show and improve the effect that property is bent in folding.

In addition, control respectively in the specialized range of above-mentioned formula (4) ~ (8) and mean that below the numerical value of regulation the ordered state of copper atom is well consistent the half value of the diffraction peak of each crystal face is wide.Think with the control of above-mentioned formula (1) ~ (3) and formula (9) ~ (11) in specialized range and improved under the state of the curved property of folding, the arrangement of copper atom is more consistent, curved characteristic further improves as a result.

(2) about the crystal face controlling mechanism in secondary orientation

Crystal Rotation

As mentioned above, final cold rolling process etc. rolling adds man-hour, and copper material has been applied stress under compression and the tensile stress more weak than stress under compression.Copper crystal in the copper material that is rolled produces to { rotation phenomenon of 022} face, the orientation that forms the crystal face that is parallel to rolling surface in rolling processing development is mainly the { rolling texture of 022} face by the rolling stress that adds man-hour.At this moment, as mentioned above, according to the ratio of stress under compression with tensile stress, towards { the path changing that the 022} face rotates.About this point, use Fig. 5 to describe.

Fig. 5 is the antipole point diagram of the fine copper shaped metal quoted from following technical literature (first), (a) for showing the antipole point diagram of the Crystal Rotation direction that tensile deformation causes, (b) for showing the antipole point diagram of the Crystal Rotation direction that compression set causes.In addition, in the antipole point diagram, will { the 002} face be designated as that { the 001} face, { the 022} face is designated as { 011} face.That is, and the 002} face with as be parallel to the minimum value of the face of 002} face the 001} face represents, and the 022} face with as be parallel to the minimum value of the face of 022} face { the 011} face is represented.

The kind Co., Ltd. in the long Shima of (first) editor Shanxi one, " texture (collection closes Group Woven) ", ball, clear and on January 20th, 59, the 96th page Fig. 2 .52 (a), (c)

As shown in Figure 5, the copper crystal in the copper material when tensile deformation only towards the 111} face rotates, and when compression set only towards { the 011} face rotates.In the rolling processing, owing to compress composition and be drawn into the distortion that branch merges, therefore, the Crystal Rotation direction is so not simple.But owing to compare with being drawn into branchs, the compression composition occupies advantage, deforms and is rolled processing, therefore can take place usually towards the { Crystal Rotation of 011} face, and according to compressing composition and stretching components in proportions, to { the 111} face also can rotate a part.At this moment, because compression composition one side occupies advantage, therefore, to { crystal that the 111} face has taken place to rotate also can take place to { the Crystal Rotation that the 011} face returns.In addition, opposite with it, towards { crystal that the 011} face has carried out rotating, having arrived that { crystal of 011} face sometimes also can be towards { the 133} face, { the 111} face rotates because of the stretching composition.

Think thus, if compression composition and stretching composition are keeping the compression composition mixing in the relation of stretching composition and cause Crystal Rotation in existing, then finally become the distribution of the crystal face in main orientation shown in the antipole point diagram of Fig. 6 and secondary orientation.Because compression composition〉the stretching composition, therefore the crystal face in final main orientation becomes { 011} face, and think that the result of the Crystal Rotation that causes because of the mixing of compression composition and stretching composition is that the crystal face in secondary orientation becomes { 001} face, { 113} face, { 111} face, { 133} face.

Here, Fig. 6 is shown as the crystal face that only is distributed with above-mentioned particular orientation, and it be the reasons are as follows.Because copper is the crystal of face-centred cubic structure, therefore, in the X-ray diffraction that utilizes 2 θ/θ method is measured, if { h of hkl} face, k, l all are odd number value or all are even number value, then do not occur as diffraction peak.If h, k, l are odd number value and the existence that mixes of even number value, then disappear according to the extinction rule diffraction peak, can not measure.Therefore, when showing the formation of the rolled copper foil that above-mentioned embodiment etc. is related, { 001} face ({ 002} face), { 113} face, { 111} face and { the secondary orientation of 133} face is stipulated to occur as diffraction peak.Because according to the result of the above embodiments etc., the effect of this formation also is clear and definite, if therefore consider the crystal face in the above-mentioned secondary orientation of enumerating, then can be described as fully.

Control by degree of finish

As known from the above, if be the ratio that prerequisite is adjusted compression composition and stretching composition with stress under compression＞tensile stress, then towards the { path changing that the 022} face rotates.Particularly, the compression composition is more big, then more is easy to via { the 002} face, { the 113} face, the stretching composition is more big, then more is easy to via { 111} face and { 133} face.The crystal face in main secondary orientation become the 002} face, the 113} face, the 111} face and the 133} face be because, fail fully to { the above-mentioned crystal face that the 022} face rotates remains in the copper material, thereby by compressing the adjustment of composition and stretching composition in the final cold rolling process, can adjust the ratio of the crystal face in each residual in the copper material secondary orientation.

Particularly, compression composition and stretching composition can be controlled by changing the rolling rolling condition that adds per 1 passage in man-hour.Particularly, as attempting among above-mentioned embodiment, the embodiment, for example can be conceived to the variation of the degree of finish of per 1 passage.

In order to improve the degree of finish of per 1 passage, for example there is increase rolling load (roller load) to roll the method as the copper material of rolling object, under this situation, it is big that stress under compression becomes.Therefore, the rotation path of crystal is { 002} face, { 113} face, and towards { the 022} face rotates.

On the other hand, also having with stress under compression＞tensile stress is prerequisite, by increasing the stretching composition and making the copper material attenuation improve the method for degree of finish.Owing to increased the stretching composition, therefore, the rotation path of crystal is { 111} face, { 133} face, and towards { the 022} face rotates.In addition, can think that rolling back is remaining in copper material { in the 133} face, to be comprised by stretching composition in the rotation process of crystal resulting and arrive for the time being by the compression composition that { crystal of 022} face turns to the { face of 133} face again by the stretching composition.In addition, the variation of the degree of finish that causes because of tensile stress is compared little with the situation that increases compression load.That is, stress under compression is bigger to the contribution of degree of finish.

Control by neutrality point

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

As mentioned above, the control elements as the neutral position of putting of control in per 1 passage has the place ahead tension force, rear tension force, roll speed (velocity of rotation of roller), roller footpath, degree of finish, rolling load etc.The multiple combination of these control elementss can be made the position of neutral point change.

The position of described neutral point can be from several observed values by calculating.That is, at first, in the relation of following formula that with following technical literature (second) is reference,

The composition of the composition+force of compression of tension force=2 * shear yield stress ... (C)

Make the force of compression composition bigger than tension force composition, further, use formula (C) calculates directly the conditional equilibrium of roll speed and roller, be the position of neutrality point of the contact surface of the rolling roller that adds man-hour and copper material.In addition, for neutrality point in detail, with reference to following technical literature (second).

(second) Japanese plastic working association compiles, " Technology of Plastic Processing series 7 plates are rolling ", Corona company, the 14th page, the 27th page (3.3), the 28th page

Parameter when above-mentioned formula (C) is calculated is above-mentioned control elements, but in these key elements, can and variable will usually consider polytype control method by key element how to select to fix.In above-mentioned embodiment, embodiment, degree of finish is controlled the position of neutral point as variable control elements, but also can use the control elements beyond the degree of finish to control.

In addition, above-mentioned control elements is relevant with the formation of roller mill, and the position control of neutral point exists with ... the specification of roller mill greatly.Particularly, because of the difference of formation of the roller of the combining and configuring of the sum of the progression of roller, roller, roller, each roller footpath, material, condition of surface (surfaceness) etc. etc., be created in the difference of aspects such as applying method to the stress under compression of copper material, frictional coefficient.If roller mill difference, related its absolute value of each control elements of the condition of then enumerating in the above-described embodiment are also different, therefore can adjust each roller mill aptly.In addition, even identical roller mill, if the material difference of the condition of surface of Rolling roller, Rolling roller, then the absolute value of each control elements also can be different.Therefore, even identical roller mill also can suit to adjust according to state separately.

Claims

1. a rolled copper foil is characterized in that, its be possess major surfaces, have with cold rolling process a plurality of crystal faces of described major surfaces in parallel, final after rolled copper foil before the recrystallization annealing operation,

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

Will to described major surfaces utilize 2 θ/θ method carry out X-ray diffraction measure and obtain, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _{{ 022}}, I _{{ 002}}, I _{{ 113}}, I _{{ 111}}And I _{{ 133}}The time,

I _{113}≤6.0，

I _{{ 111}}≤ 6.0, and

I _{133}≤6.0，

The wide FWHM that is made as respectively of half value with the diffraction peak of described each crystal face _{{ 022}}, FWHM _{{ 002}}, FWHM _{{ 113}}, FWHM _{{ 111}}And FWHM _{{ 133}}The time,

FWHM _{002}≤0.60，

FWHM _{022}≤0.50，

FWHM _{113}≤0.50，

FWHM _{{ 111}}≤ 0.50, and

FWHM _{133}≤0.70。

2. rolled copper foil according to claim 1, it is characterized in that, will by about have the 022} face, the 002} face, the 113} face, the 111} face and the relative intensity of the standard diffraction peak of described each crystal face of putting down in writing in the JCPDS card of the powder copper of 133} face or the ICDD card obtains, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}The time,

I _{113}/I _0{113}≤0.70，

I _{{ 111}}/ I _0{111}≤ 0.12, and

I _{133}/I _0{133}≤1.3。

3. rolled copper foil according to claim 1 and 2 is characterized in that, I _{{ 002}}〉=7.5.

4. according to each described rolled copper foil in the claim 1 ~ 3, it is characterized in that, will by about have the 022} face, the 002} face, the 113} face, the 111} face and the relative intensity of the standard diffraction peak of described each crystal face of putting down in writing in the JCPDS card of the powder copper of 133} face or the ICDD card obtains, with aggregate value become that 100 mode converts and the diffraction peak intensity of described each crystal face than being made as I respectively _0{022}, I _0{002}, I _0{113}, I _0{111}And I _0{133}The time,

I _{002}/I _0{002}≥0.30。

5. according to each described rolled copper foil in the claim 1 ~ 4, it is characterized in that, is principal constituent with the tough pitch copper of stipulating among the oxygen free copper stipulated among the JIS C1020 or the JIS C1100.

6. according to each described rolled copper foil in the claim 1 ~ 5, it is characterized in that, be added with in silver, boron, titanium, the tin at least any.

7. according to each described rolled copper foil in the claim 1 ~ 6, it is characterized in that, is that described final cold rolling process more than 90% makes that thickness is below the 20 μ m by total degree of finish.

8. according to each described rolled copper foil in the claim 1 ~ 7, it is characterized in that, be used for flexible printing patch panel.