CN103255313A

CN103255313A - Rolled copper foil

Info

Publication number: CN103255313A
Application number: CN2013100489761A
Authority: CN
Inventors: 室贺岳海; 关聪至
Original assignee: Saikos Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2012-02-17
Filing date: 2013-02-07
Publication date: 2013-08-21
Anticipated expiration: 2033-02-07
Also published as: KR102001959B1; KR20130095204A; JP5126434B1; JP2013170278A; CN103255313B

Abstract

The invention relates to a rolled copper foil which exhibits excellent bending performance after a recrystallization annealing process. With 100% as a total, the diffraction peak intensity ratios of a {022} surface, a {113} surface, a {111} surface, a {133} surface and a {002} surface, all parallel to a main surface, are respectively set to be I {022}, I {002}, I {113}, I {111} and I {133}. With 100% as a total, the diffraction peak intensity ratios of powder coppers having the {022} surface, the {113} surface, the {111} surface, the {133} surface and the {002} surface are respectively set to be I0 {022}, I0 {113}, I0 {111}, I0 {133} and I0 {002}. I {022}/I0 {022} >=7.0, I {113}/I0 {113} >=0.40, I {111}/I0 {111}>=0.090, and I {133}/I0 {133} =1.4.

Description

Rolled copper foil

Technical field

The present invention relates to rolled copper foil, particularly for the rolled copper foil of flexible printing patch panel.

Background technology

Flexible printing patch panel (FPC:Flexible Printed Circuit) is because thin and pliability is excellent, thereby to the degree of freedom height of the installation form of electronics etc.Therefore, the bending part of Collapsible mobile telephone, most FPC that use in 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, for the rolled copper foil that uses as FPC, its wiring material, require excellent curved characteristic.

FPC makes through hot rolling, operation such as cold rolling with rolled copper foil, by caking agent or directly fit by heating etc. with the basement membrane (base material) of the FPC that is constituted by resins such as polyimide, and surface working such as 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 improves more significantly.Therefore, for example, in above-mentioned manufacturing process, adopt following manufacture method: use the rolled copper foil after cold rolling, avoid extending, in the distortion such as wrinkle, the cutting rolled copper foil, it is overlapped after on the base material, the recrystallization annealing of double as rolled copper foil and heating, thus make rolled copper foil and base material driving fit carry out integrated.

Up to the present, manufacturing process with above-mentioned FPC is prerequisite, rolled copper foil, its manufacture method to the curved characteristic excellence have been carried out various researchs, much reported the following fact: on the surface of rolled copper foil, as the cubes orientation { 002} face ({ 200} face) reaches then all the more, and curved characteristic more improves.

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

In addition, for example in the 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 ₀The rolled copper foil that 〉=40 cubes texture is significantly flourishing.

In addition, for example in the 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 each passage is controlled to be 15%～50%.Thus, after recrystallization annealing, obtain grain orientation state as described below, that is, by the X-ray diffraction pole graph measure the rolling surface obtain the 111} face with respect in the face of 200} face orientation degree Δ β be below 10 ° and in the rolling surface as cubes texture { diffraction peak intensity [a] after the stdn of 200} face is with { ratio of the diffraction peak intensity [b] after the crystal region stdn with twin crystal relation of 200} face is [a]/[b] 〉=3.

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

The 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

Invent problem to be solved

But, as above-mentioned patent documentation 1～3, even show more cubes texture, in adopting the rolled copper foil of polycrystalline structure as cubes texture { the 002} face can not account for 100% yet.That is, in rolled copper foil except main orientation { the 002} face, { the 113} face, { the 111} face, { crystal face in secondary orientation such as 133} face is not controlled, but a plurality of mixing exists.

In recent years, along with miniaturization, the slimming of electronics, the situation of assembling FPC increases in little space, must guarantee the reliability of the performance of FPC, its wiring material in littler space.And adapt with it, the requirement of the curved characteristic of the rolled copper foil that becomes wiring material is also improved, only be conceived to main orientation { method that the 002} face improves the so above-mentioned patent documentation 1～3 of the ratio of cubes texture has the limit.

The objective of the invention is to, a kind of rolled copper foil that can have excellent curved characteristic after the recrystallization annealing operation is provided.

Be used for solving the method for problem

According to the 1st mode of the present invention, a kind of rolled copper foil is provided, it is for possessing major surfaces, and after having a final cold rolling process with a plurality of crystal faces of described major surfaces in parallel, the rolled copper foil before the recrystallization annealing operation, described a plurality of crystal face comprises { 022} face, { 113} face, { 111} face, { 133} face and { the 002} face will be measured institute by the X-ray diffraction that uses 2 θ/θ method to described major surfaces and be obtained, is that the diffraction peak intensity of 100 described each crystal face that converted compares and is made as I respectively with aggregate value _{{ 022}}, I _{{ 113}}, I _{{ 111}}, I _{{ 133}}And I _{{ 002}}, will by about have the 022} face, the 113} face, the 111} face, the 133} 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 002} face or the ICDD card obtained, be that the diffraction peak intensity of 100 described each crystal face that converted compares and is made as I respectively with aggregate value _0{022}, I _0{113}, I _0{111}, I _0{133}And I _0{002}The time,

I _{022}/I _0{022}≥7.0、

I _{113}/I _0{113}≥0.40、

I _{{ 111}}/ I _0{111}〉=0.090 and

I _{133}/I _0{133}≥1.4。

According to the 2nd mode of the present invention, provide a kind of as the described rolled copper foil of the 1st mode, wherein, I _{{ 002}}/ I _0{002}≤ 0.25.

According to the 3rd mode of the present invention, a kind of as the 1st mode or the described rolled copper foil of the 2nd mode are provided, wherein, be principal constituent with the tough pitch copper of stipulating among the oxygen free copper stipulated among the JIS C1020 or the JIS C1100.

According to the 4th mode of the present invention, the described rolled copper foil of arbitrary mode in a kind of as the 1st mode～the 3rd mode is provided, wherein, added in silver, boron, titanium, the tin at least any.

According to the 5th mode of the present invention, the described rolled copper foil of arbitrary mode in a kind of as the 1st mode～the 4th mode is provided, wherein, be described final cold rolling process more than 90% by total degree of finish, making thickness is below the 20 μ m.

According to the 6th mode of the present invention, the described rolled copper foil of arbitrary mode in a kind of as the 1st mode～the 5th mode is provided, wherein, be used for flexible printing patch panel.

The effect of invention

According to the present invention, provide a kind of rolled copper foil that can after the recrystallization annealing operation, have excellent curved characteristic.

Description of drawings

Fig. 1 is for showing the schema of the rolled copper foil manufacturing process that an embodiment of the invention are related.

Fig. 2 (a) is the X-ray diffractogram of the related rolled copper foil of the embodiment of the invention for the measurement result of the X-ray diffraction of use 2 θ/θ method, (b) is the X-ray diffractogram of the related rolled copper foil of comparative example.

Fig. 3 is the synoptic diagram of the slip bend test device of the curved characteristic of the related rolled copper foil of the mensuration embodiment of the invention.

Fig. 4 is the antipole point diagram of fine copper shaped metal, (a) for showing the antipole point diagram of the crystallization turning direction that causes because of tensile deformation, (b) for showing the antipole point diagram of the crystallization turning direction that causes because of compression set.

Fig. 5 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 transfer part

14 vibration driving bodies

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. have also carried out the various experiments for the occupation rate increase that makes the cubes orientation.And, confirmed by experimental result up to the present, behind final cold rolling process, exist { 022} looks like the recrystallization annealing operation of fruit by thereafter by modified one-tenth recrystallize, then becomes { 002} face, i.e. cubes orientation.That is, preferably behind final cold rolling process, before the recrystallization annealing operation, { the 022} face becomes main orientation.

And on the other hand; because rolled copper foil is polycrystalline; therefore; rolling surface integral body can not account for 100% by a crystal face; for example under the state behind the final cold rolling process; except { the 022} face, also mixing having that a plurality of { the 113} face, { the 111} face, { crystal face in secondary orientation such as 133} face thinks that the crystal grain with these a plurality of crystal faces can produce various influences to every characteristic of rolled copper foil as main orientation.Therefore, the crystal face in the secondary orientation that the inventor etc. are conceived to up to the present to be considered to useless when constantly can research in the occupation rate of keeping main orientation and guarantee high curved characteristic, makes the crystal face in these secondary orientation help the further raising of curved characteristic.

The result of such further investigation, discoveries such as the inventor: for { 113} face, { 111} the face, { ratio of the crystal face in secondary orientation such as 133} face, by the deviation that control is compared with the crystal face ratio in the secondary orientation of standard of copper, can further improve the curved characteristic of rolled copper foil.

The invention that the present invention finishes for the above-mentioned opinion of finding based on contriver etc.

An embodiment of the invention

(1) formation of rolled copper foil

The formations such as crystalline structure of the rolled copper foil that relevant an embodiment of the invention are related at first, are described.

The summary of rolled copper foil

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.Namely, the rolled copper foil that present embodiment is related, for example, by total degree of finish be more than 90%, more preferably the final cold rolling process more than 94% to constitute thickness be below the 20 μ m, thereby the flexual wiring material purposes that is used for FPC,, as described above for example implement the recrystallization annealing operation of bonding process of the base material of double as and FPC, and attempt to possess excellent curved characteristic by recrystallize thereafter.

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, for example can contain the oxygen of several ppm degree.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.Also trace adds the interpolation material of silver regulations such as (Ag) and makes the lower concentration copper alloy in oriented these copper materials, thereby makes the situation of the rolled copper foil of having adjusted every characteristics such as thermotolerance.With regard to the related rolled copper foil of present embodiment, can comprise fine copper and lower concentration copper alloy the two, raw-material copper material, add material the effect of present embodiment exerted an influence hardly.

With regard to the total degree of finish in the final cold rolling process, the thickness of the processing object thing before the final cold rolling process (sheet material of copper) is made as T _B, the thickness of the processing object thing behind the final cold rolling process is made as T _AThe time, with total degree of finish (%)=[(T _B-T _A)/T _B] * 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, { 113} face, { 111} face, { 133} face and { 002} face.{ the 022} face becomes the main orientation in the rolling surface, and other each crystal face is secondary orientation.So, control becomes in rolling surface, and each crystal face has the occupation rate of regulation respectively.

Particularly, for the occupation rate of each crystal face, the deviation that control is compared with the standard crystal face occupation rate of copper.The occupation rate of each crystal face roughly with by X-ray diffraction is measured the diffraction peak intensity of each crystal face of obtaining than equating that above-mentioned deviation can recently be stipulated, control by diffraction peak intensity.The diffraction peak intensity ratio of each crystal face can followingly be obtained.

Namely, for the rolling surface of the related rolled copper foil of present embodiment, it is 100 such ratios that the diffraction peak intensity of the above-mentioned 5 kinds of crystal faces that will be measured 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.In the diffraction peak intensity ratio of each crystal face, as representative, below illustrate and ask { the conversion formula (A) of the diffraction peak intensity ratio of 022} face.Here, the diffraction peak intensity ratio with each crystal face in the rolled copper foil is made as I respectively _{{ 022}}, I _{{ 113}}, I _{{ 111}}, I _{{ 133}}And I _{{ 002}}, the diffraction peak intensity of each crystal face is made as I ' respectively _{{ 002}}, I ' _{{ 113}}, I ' _{{ 111}}, I ' _{{ 133}}And I ' _{{ 002}}

Several 1

In addition, as the standard diffraction peak of copper, for example can enumerate and have { 022} face, { 113} face, { 111} face, { 133} face and the { diffraction peak of the powder copper of 002} face.For example, in JCPDS (JCPDS, 40836) or ICDD (joint committee Joint Committee for Powder Diffraction Standards) card (card number number:, International Center for Diffraction Data) in the card, records the relative intensity of related diffraction peak.

The relative intensity of the standard diffraction peak of above-mentioned 5 kinds of crystal faces can be amounted to that to be converted into aggregate value be 100 such ratios, powder copper is obtained the diffraction peak intensity ratio of each crystal face, and with they benchmark values as the deviation of the diffraction peak intensity ratio of each crystal face of regulation the rolling Copper Foil.In the diffraction peak intensity ratio of each crystal face, as representative, below illustrate and ask { the conversion formula (B) of the diffraction peak intensity ratio of 022} face.Here, the diffraction peak intensity ratio with each crystal face in the powder copper is made as I respectively _0{022}, I _0{113}, I _0{111}, I _0{133}And I _0{002}, the diffraction peak intensity of each crystal face is made as I respectively ₀' _{{ 022}}, I ₀' _{{ 113}}, I ₀' _{{ 111}}, I ₀' _{{ 133}}And I ₀' _{{ 002}}

Several 2

In the related rolled copper foil of present embodiment, there is the relation of all setting up than following formula (1)～(4) that are benchmark value with the diffraction peak intensity of each crystal face in the above-mentioned powder copper.

I _{022}/I _0{022}≥7.0···(1)

I _{113}/I _0{113}≥0.40···(2)

I _{111}/I _0{111}≥0.090···(3)

I _{133}/I _0{133}≥1.4···(4)

In addition, in the related rolled copper foil of present embodiment, preferred following formula (5) is set up.

I _{002}/I _0{002}≤0.25···(5)

The effect of crystalline structure

By last, the related rolled copper foil of present embodiment constitutes possesses excellent curved characteristic after the recrystallization annealing operation.

Namely, as above-mentioned, the rolled copper foil before the recrystallization annealing operation the 022} face after the recrystallization annealing operation to { the 002} face changes, thereby the curved characteristic of rolled copper foil is improved.According to the result of embodiment described later etc., in order to produce such variation, with respect to the powder copper that becomes benchmark { diffraction peak intensity of 022} face compares I _0{022}, rolled copper foil { diffraction peak intensity of 022} face compares I _{{ 022}}Be necessary for more than the deviation amplitude of regulation, namely, for example need to satisfy above-mentioned formula (1).At this moment, the value of formula (1) is more big more preferred, but rolled copper foil is polycrystalline, and { 100% this point that the 022} face can not account for rolling surface becomes prerequisite.

In addition, with the recrystallization annealing operation before { 113} face, { the 111} face and { diffraction peak intensity of 133} face compares I of rolled copper foil _{{ 113}}, I _{{ 111}}And I _{{ 133}}The deviation amplitude compared of the benchmark value accumulation degree that can be illustrated in the processing strain that rolled copper foil bears in the final cold rolling process grasp.That is, when satisfying above-mentioned formula (2)～(4), we can say at { 113} face, { 111} face and { accumulated more processing strain in each crystal grain of 133} face.According to the inventor's etc. investigation, Ji Lei processing strain can promote the recrystallize of rolled copper foil in the recrystallization annealing operation like this, makes more { the 002} length of looking unfamiliar.At this moment, the value of formula (2)～(4) is more big more preferred, but { the 022} face is that main orientation becomes prerequisite.

And on the other hand, the someone says that { the 002} face is difficult to accumulation processing strain.Therefore, with the recrystallization annealing operation before rolled copper foil { diffraction peak intensity of 002} face compares I _{{ 002}}The deviation amplitude compared of benchmark value do not represent the accumulation degree of above-mentioned such processing strain, but can represent { how many amounts of 002} face is grasped with respect to the powder copper that becomes benchmark.When satisfying above-mentioned formula (5), we can say rolled copper foil { amount of 002} face is suppressed to less state.Investigation according to inventor etc., by after suppressing final cold rolling process, before the recrystallization annealing operation the amount of 002} face, processing should tail off { crystal grain of 002} face can suppress to hinder the growth that the recrystallize because of the crystal grain of the crystal orientation with other brings.Therefore, the value of formula (5) is more little more preferred.

Yet, for example in TOHKEMY 2009-185376 communique, for { the 002} face has been reported to have to promote in the recrystallization annealing operation from { 022} is towards { the function that the 002} face changes.But, in TOHKEMY 2009-185376 communique, its purpose is, total degree of finish in the final cold rolling process is being suppressed under less than 93%, preferably less than 90% state, for example obtain with above-mentioned patent documentation 1～3 in the high curved characteristic that is equal to mutually of the rolled copper foil of viewed high degree of finish.

In the present embodiment, as mentioned above, its purpose is, { the 002} face has in the danger that hinders recrystallize under being based on the condition of high degree of finish, make the curved characteristic raising except improving total degree of finish, also control comprises that { the crystal face ratio in the secondary orientation of 002} face is compared and further improved curved characteristic with patent documentation 1～3, TOHKEMY 2009-185376 communique.

More than, satisfy formula (1)～(4) and, preferably satisfy the investigation that act as result based on embodiment described later etc. shown in crystalline structure above-mentioned of formula (5) and the effect learnt.Namely, with regard to the related rolled copper foil of present embodiment, if the diffraction peak intensity of each crystal face ratio has satisfied the aforementioned proportion relational expression before the recrystallization annealing operation, then after the recrystallization annealing operation, possess excellent curved characteristic.Like this, in order after the recrystallization annealing operation, to obtain high curved characteristic, as long as behind the final cold rolling process of control, each crystal orientation of the rolled copper foil before the recrystallization annealing operation.

(2) manufacture method of rolled copper foil

Next, use Fig. 1 that the manufacture method of the rolled copper foil that relevant an embodiment of the invention are related is described.Fig. 1 is the schema of the manufacturing process of the related 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, thereby prepared ingot bar (ingot casting).Ingot bar for example forms has the tabular of specific thickness, Rack.Also 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.

Can thermotolerance for example be arranged by adding in above-mentioned every characteristic that material adjusts.As mentioned above, for the FPC rolled copper foil, the recrystallization annealing operation that is used for obtaining high curved characteristic for example the applying of the base material of double as and FPC operation and carry out.Heating temperature during applying for example waits to set 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, a wider range of temperature condition and be varied.For the softening temperature that makes rolled copper foil and the Heating temperature of so setting adapt, there is interpolation can adjust the situation of the stable on heating interpolation material of rolled copper foil.

As the ingot bar that uses in the present embodiment, following table 1 illustration add material ingot bar, added the ingot bar of the interpolation material of several types.

Table 1

In addition, as the interpolation material shown in the above-mentioned table 1, other interpolation material, improving or reducing in the typical example of stable on heating interpolation material, 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 being arranged.Perhaps, have and add Ag as the 1st adding element, adding in the above-mentioned element any or multiple 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.

In addition, the ingot bar composition also remains unchanged in through the rolled copper foil behind the final cold rolling process S40 described later substantially, adds in ingot bar when adding material, and 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 by copper material, interpolation material.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 after the work hardening is implemented anneal with sheet material annealing to implementing cold rolling, thereby make work hardening obtain relaxing.By with its stipulated number repeatedly, be called as the copper bar of " blank ".In copper material, 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 ".

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 processing strain that is caused by above-mentioned each operation, for example implements handling under the equal substantially temperature condition with Full Annealing.

Final cold rolling process S40

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

In addition, every repeat repeatedly cold rolling, annealing blank attenuation, corresponding to this, advantageous applications is the technology of patent documentation 3 for example, and the degree of finish of per 1 time (1 passage) is slowly diminished., 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 thickness of the processing object thing after rolling is 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 is represented in] * 100.

Rollingly add man-hour, processing object things such as annealing blank for example are 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.In order to process the processing object thing thinner, must make stress under compression＞tensile stress.As mentioned above, by adjusting the degree of finish of per 1 passage, be prerequisite with stress under compression＞tensile stress for example, can adjust the ratio of each stress component (compression composition and stretching composition).

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

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.

Like this, the compression pressure when adjusting final cold rolling process S40 aptly and the stress equilibrium of tensile stress can be controlled the balance of the diffraction peak intensity of each crystal face, namely control the diffraction peak intensity ratio, can be met the rolled copper foil of above-mentioned formula (1) ~ (5).

Particularly, the stress of the copper crystal in the copper material during owing to rolling process such as the final cold rolling process S40 phenomenon that rotates, by several paths to { the 022} face changes.It is more big that stress under compression becomes, more easy of { the 002} face, { it is more big that 113} face, tensile stress become, more easy of { 111} face, { 133} face, and respectively to { the 022} face changes.

Namely, above-mentioned formula (1) has shown at least and to have arrived { the ratio of the crystal grain of 002} face as final orientation in the moment that finishes final cold rolling process S40.In addition, above-mentioned formula (2) has shown that stress under compression is strong.And above-mentioned formula (3), (4) have shown that tensile stress is stronger when being prerequisite with stress under compression＞tensile stress.

In addition, if observe above-mentioned formula (5), show a little less than the stress under compression though can be understood as, can not lump together.Satisfying the state of formula (5) can think: arrive behind the 002} face further to as before crystal orientation { situation that the 022} face rotates, arrive earlier that { crystal grain of 002} face is got back to the situation of original crystal orientation etc. under the counter rotating effect temporarily.If the state that becomes formula (5) is to { result that the 022} face rotates then can make to arrive that { crystal grain of 022} face increases, and has demonstrated the further increase that helps by the resulting value of above-mentioned formula (1), is conducive to obtain the effect of high curved characteristic.If the state that becomes formula (5) turns back to the result of original crystal orientation under the counter rotating effect, then when being prerequisite with stress under compression＞tensile stress, shown that tensile stress is stronger.

So, when the position control by the size control of the degree of finish in each passage, neutral point waits to adjust the stress equilibrium of stress under compression and tensile stress, implement final cold rolling process S40, thus the rolled copper foil that can be met above-mentioned formula (1)～(4) and preferably satisfy formula (5).Therefore, after the recrystallization annealing operation, can obtain having the rolled copper foil of excellent curved characteristic.

Surface treatment procedure S50

To implement the surface treatment of regulation through the copper bar of above operation.By the above-mentioned rolled copper foil of making 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 that present embodiment is related is cut into the size of regulation, for example fits with the base material of the FPC that is made of resins such as polyimide and forms CCL (copper clad laminate, Copper Clad Laminate).At this moment, can use by caking agent and fit to form the method for 3 layer material CCL and directly do not fit to form any in the method for 2 layer material CCL by caking agent.When using caking agent, by heat treated caking agent is solidified, make rolled copper foil and base material driving fit and carry out integrated.When not using caking agent, by heating, pressurization, make the direct driving fit of rolled copper foil and base material.Heating temperature, time can be according to the suitable selections such as solidification value of caking agent, base material, for example can be in the temperature below 400 ℃ more than 150 ℃, carry out 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, through final cold rolling process S40 and the rolled copper foil of state after the work hardening softens and recrystallize by above-mentioned heating.That is, on base material the CCL operation double as of applying rolled copper foil to the recrystallization annealing operation of rolled copper foil.

By making CCL operation double as recrystallization annealing operation, thereby in the operation before fitting to rolled copper foil on the base material, carrying out that can be behind final cold rolling process S40 handle rolled copper foil under the state of work hardening, can be difficult for producing distortion such as elongation when fitting to rolled copper foil on the base material, wrinkle, bending.

In addition, above-mentioned such the softening of rolled copper foil shown, obtained having the rolled copper foil of recrystallized structure by the recrystallization annealing operation.Particularly, as main orientation { diffraction peak intensity of 022} face compares I _{{ 022}}Satisfy above-mentioned formula (1), { the 022} face can be to { the 002} face changes.Thus, can obtain the rolled copper foil of curved characteristic excellence.

In addition, as { 113} face, { the 111} face and { diffraction peak intensity of 133} face compares I in secondary orientation _{{ 113}}, I _{{ 111}}And I _{{ 133}}Satisfy above-mentioned formula (2)～(4), above-mentioned each crystal face is in the high state of energy that greatly accumulation has the processing strain.Therefore, the processing strain of accumulation is with { the processing strain of 022} face, the recrystallize of promotion rolled copper foil.

In addition, be present in the rolled copper foil before the recrystallization annealing operation { diffraction peak intensity of 002} face compares I _{{ 002}}Satisfy above-mentioned formula (5), rolled copper foil { amount of 002} face is controlled as less state.Therefore, { the 002} face suppresses to hinder by above-mentioned each crystal face promotion recrystallize.

So, when satisfying above-mentioned formula (1)～(4) and preferably satisfying formula (5), the rolled copper foil after the recrystallization annealing operation can have excellent curved characteristic.Namely, in order after the recrystallization annealing operation, to obtain high curved characteristic, for the rolled copper foil behind final cold rolling process S40, before the recrystallization annealing operation, as long as control each crystal orientation in the mode that satisfies the above-mentioned relation formula.

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 to be used method such as for example etching form copper wiring etc. that described distribution forms operation; described surface treatment procedure is the surface treatments such as plating processing that implement to be used for improve copper wiring and the connection reliability of other electronic unit, and it is that the mode with the part on the copper wiring that is covered forms protective membranes such as solder resist in order to protect copper wiring etc. that described protective membrane forms operation.

Used the FPC of the related rolled copper foil of present embodiment by above manufacturing.

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 suitable interpolation material of selecting of the every characteristic that can adjust as required.

In addition, in the above-described embodiment, the CCL operation double as in the FPC manufacturing process is to the recrystallization annealing operation of 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, can needing be used for the purposes of high curved characteristic.For the thickness of rolled copper foil, according to the various uses headed by the FPC purposes, also can make it surpass 20 μ m etc.

In addition, in order to play effect of the present invention, above-mentioned whole operations of enumerating are not necessary.The various conditions of enumerating among above-mentioned embodiment, the embodiment described later are illustration also, can suit to change.

Embodiment

Next, with comparative example embodiments of the invention are described.

(1) rolled copper foil of use oxygen free copper

At first, make to use the related rolled copper foil of the embodiment 1 ~ 7 of oxygen free copper and comparative example 1 ~ 7 as follows, respectively they are carried out various evaluations.

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 related rolled copper foil of embodiment 1 ~ 7 and comparative example 1 ~ 7.But, for comparative example 1 ~ 7, comprise processing that drops on outside the formation etc.

Particularly, prepare in oxygen free copper, to have dissolved the Ag of specified amount 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 aimed concn 150ppm, analytical value is 139ppm ~ 163ppm, all is suppressed in the deviation in 150ppm ± 15ppm (10%) degree.This contains the situation about several ppm ~ tens ppm as inevitable impurity in as the oxygen free copper of main raw material except there being Ag, deviation in the various reasons such as deviation during owing to cast billets, ± 15ppm degree is normal conditions 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 keep about 2 minutes process annealing operation 700 ℃ ~ 800 ℃ temperature, make copper bar (blank), by keep about 1 minute blank anneal operation in about 750 ℃ temperature, obtain the blank of annealing.Here, temperature condition of each annealing operation etc. adapts with the thermotolerance of the anaerobic copper material of the Ag that contains 139ppm ~ 163ppm.Need to prove, for forming identical copper material, adopt different temperature condition in each annealing operation, is owing to the thickness of thermotolerance along with copper material changes, and when copper material is thin, can reduce temperature.

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 ~ 7.Following table 3 shows the condition of final cold rolling process.

Table 3

* 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, along with from epimere to hypomere thickness of slab attenuation successively, 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.The position of the neutrality point shown in right hurdle (mm) is represented with roller and the length from the outlet side end to neutrality point as the contact surface of the annealing blank of processing object thing.In addition, in order to obtain excellent curved characteristic, in embodiment 1 ~ 7 and comparative example 1 ~ 7 whole, imposing a condition makes that the total degree of finish in final cold rolling process is 95%.By the related rolled copper foil of the above making thickness embodiment 1 ~ 7 that is 12 μ m and comparative example 1 ~ 7.

Then, each rolled copper foil to making as described above carries out following evaluation.

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

At first, the rolled copper foil related to embodiment 1 ~ 7 and comparative example 1 ~ 7 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, Fig. 2 (a) shows the X-ray diffractogram of embodiment 1, and Fig. 2 (b) shows the X-ray diffractogram of comparative example 1.

Table 4

Next, { 022} face, { 113} face, { 111} face, { the 133} face and { it is 100 such ratios that the diffraction peak intensity of 002} 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.For the related rolled copper foil of embodiment 1～7 and comparative example 1～7, show that in following table 5 diffraction peak intensity by above-mentioned each crystal face of obtaining compares I _{{ 022}}, I _{{ 113}}, I _{{ 111}}, I _{{ 133}}And I _{{ 002}}Value.

Table 5

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

Crystal face	I _{022}	I _{113}	I _{111}	I _{133}	I _{002}
						Embodiment-1	79.1	3.6	4.7	6.6	6.0
Embodiment-2	73.0	7.6	7.8	9.0	2.6
						Embodiment-3	75.2	4.5	7.3	7.0	6.0
Embodiment-4	77.2	4.8	4.7	7.5	5.8
						Embodiment-5	80.2	3.6	6.3	7.9	2.0
Embodiment-6	79.6	5.2	6.7	6.6	1.9
						Embodiment-7	79.6	6.6	4.8	6.7	2.3
Comparative example-1	75.4	5.5	4.5	3.9	7.5
						Comparative example-2	74.3	9.7	1.9	7.9	6.2
Comparative example-3	75.4	4.5	1.8	6.3	12.0
						Comparative example-4	79.6	6.8	2.1	5.3	6.2
Comparative example-5	72.0	3.0	1.9	3.2	19.9
						Comparative example-6	79.5	3.1	6.0	7.0	4.4
Comparative example-7	63.8	3.1	5.1	3.3	24.7

In addition, for powder copper, from the card number number: obtain the relative intensity with the standard diffraction peak of above-mentioned same each crystal face the record of 40836 JCPDS card.Namely, obtain { the 111} face is as each crystal face of 100 o'clock { 022} face, { 113} face, { 133} face and the { relative intensity separately 20,17,9,46 of 002} face.

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

Further, use the related diffraction peak intensity of the rolled copper foil shown in the table 5 than the diffraction peak intensity ratio related with above-mentioned powder copper, obtain above-mentioned formula (1)～(5) related numerical value.The epimere of following table 6 represents that the diffraction peak intensity of each crystal face of powder copper compares I _0{022}, I _0{113}, I _0{111}, I _0{133}And I _0{002}Value.In addition, hypomere is represented by the above-mentioned above-mentioned formula of obtaining (1)～(5) related numerical value.

Table 6

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

Crystal face	I _0{022}	I _0{113}	I _0{111}	I _0{133}	I _0{002}
						JCPDS card data	10.4	8.9	52.1	4.7	24.0

As mentioned above, in present embodiment and comparative example, the degree of finish of per 1 passage in final cold rolling process and neutral position of putting are changed.Thus, add man-hour cold rolling, the compression composition that puts on the processing object thing changes with the ratio of the stress component of stretching composition.Its result, the ratio vary of each crystal face, variation has also taken place in the diffraction peak intensity ratio of each crystal face shown in the table 5, the related numerical value in formula (1) ~ (5) shown in the table 6.

In addition, as shown in table 6, under the combination of each condition of embodiment 1 ~ 7, each value of formula (1) ~ (5) is all in above-mentioned specialized range.

And on the other hand, under the combination of each condition of comparative example 1 ~ 7, the whichever rolled copper foil has one or more values outside above-mentioned specialized range in each value of formula (1) ~ (5).In the table 6, show the value that departs from above-mentioned specialized range with the thick word table of being with underscore.

The flexible life test

Then, in order to investigate 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 breaking.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 グ Co., Ltd.) system is used in related test.Fig. 3 shows the synoptic diagram of the general slip bend test device 10 comprise above-mentioned FPC high speed bend test machine etc.

At first, it is that 12.5mm, length are 220mm that embodiment 1 ~ 7 and comparative example 1 ~ 7 related rolled copper foil are cut into width, imitates above-mentioned recrystallization annealing operation, and the coupons F of the thickness 12 μ m that obtain is implemented 300 ℃, 60 minutes recrystallization annealing.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, make coupons F contact and fit with vibration transfer part 13, by vibration driving body 14 vibration transfer part 13 is vibrated at above-below direction, vibration is passed to coupons F, implement flexible life and test.Condition determination as flexible life is made as 1.5mm with radius of curvature R, and stroke S is made as 10mm, and the amplitude number is made as 25Hz.Under related condition, measure each 5 of the coupons F that cut from each rolled copper foil, relatively the mean value of the number of bends till breaking.Following table 7 display result.

Table 7

As mentioned above, it is 95% final cold rolling process that each rolled copper foil has passed through total degree of finish, as shown in table 7, even comparative example 1 ~ 7 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%, simultaneously with the value of above-mentioned formula (1) ~ (5) all control in specialized range, obtained number of bends and be the more excellent curved characteristic more than 2,000,000 times.This is the value of 1.4 ~ 1.5 times of such high levels that originally has the comparative example 1 ~ 7 of high curved characteristic.

(2) rolled copper foil of use tough pitch copper

Next, 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 related rolled copper foil of the embodiment 8 of 12 μ m and comparative example 8.But, for comparative example 8, comprise processing that drops on outside the formation etc.

Ag concentration in the ingot bar of embodiment 8 and comparative example 8 is respectively 195ppm and 190ppm in 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, under 650 ℃ ~ 750 ℃ temperature, approximately kept 2 minutes, in the blank anneal operation, under about 700 ℃ temperature, approximately kept 1 minute.

For the related rolled copper foil of the embodiment 8 that makes as described above and comparative example 8, with method and the step same with the above embodiments, utilize the X-ray diffraction of 2 θ/θ method to measure.Its result, for the rolled copper foil of embodiment 8, the relation of the diffraction peak intensity of each crystal face is in the specialized range of formula (1) ~ (5).On the other hand, for the related rolled copper foil of comparative example 8, be the result who departs from specialized range.

In addition, for the related rolled copper foil of embodiment 8 and comparative example 8, to carry out the flexible life test with the same method of the above embodiments and step, its result, it is 95% final cold rolling process that each rolled copper foil has experienced total degree of finish, even comparative example 8 has also obtained 1, the curved characteristic of 706,000 such excellences more than 1,000,000 times.And on the other hand, for each embodiment in specialized range 8 all in above-mentioned formula (1) ~ (5), obtained the value of the more excellent curved characteristic of 2,392,000 such demonstration.

From the above, if the diffraction peak intensity of each crystal face than in the specialized range, then for being the rolled copper foil of main raw material with the tough pitch copper, also can obtain excellent curved characteristic.

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

Then, use added aimed concn as the Ag of 100ppm ~ 150ppm and aimed concn as the boron (B) of 50ppm ~ 200ppm as the oxygen free copper that adds material, with step and the method same with above-described embodiment, make thickness and be the related rolled copper foil of the embodiment 9 ~ 12 of 12 μ m and comparative example 9 ~ 12.But, for comparative example 9 ~ 12, comprise processing that drops on outside the formation etc.

Ag concentration in the ingot bar of embodiment 9 ~ 12 and comparative example 9 ~ 12 and B concentration in the analytical value that obtains by IPC Emission Spectrophotometer method, are respectively the interior value of scope of aimed concn shown in following table 8.

Table 8

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

For the related rolled copper foil of the embodiment 9 ~ 12 that makes as mentioned above and comparative example 9 ~ 12, measure according to the X-ray diffraction that utilizes 2 θ/θ method with the same method of above-described embodiment and step, obtain the diffraction peak intensity ratio of each crystal face.Following table 9 display result.

Table 9

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

Crystal face	I _{022}	I _{113}	I _{111}	I _{133}	I _{002}
						Embodiment-9	79.1	4.7	4.8	6.6	4.8
Embodiment-10	73.4	9.0	5.1	9.0	3.5
						Embodiment-11	74.7	5.0	7.3	7.0	6.0
Embodiment-12	78.2	3.6	5.9	7.3	5.0
						Comparative example-9	64.0	9.4	5.5	2.6	18.5
Comparative example-10	70.7	3.3	1.9	6.9	17.2
						Comparative example-11	76.8	8.4	1.8	7.3	5.7
Comparative example-12	75.9	5.9	5.1	6.1	7.0

In addition, obtain formula (1)～(5) related value by The above results, the result is shown in following table 10, and for the related rolled copper foil of embodiment 9～12, the relation of the diffraction peak intensity ratio of each crystal face is in the specialized range of formula (1)～(5).And on the other hand, for the related rolled copper foil of comparative example 9～12, whichever rolled copper foil, it is outside the above-mentioned specialized range that one or more value is arranged in each value of formula (1)～(5).In the table 10, show the value that departs from above-mentioned specialized range with the thick word table of being with underscore.

Table 10

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

In addition, for the related rolled copper foil of embodiment 9 ~ 12 and comparative example 9 ~ 12, to carry out the flexible life test with same method and the step of the above embodiments.Its result, it is 95% final cold rolling process that each rolled copper foil has experienced total degree of finish, shown in following table 11, even any one of comparative example 9 ~ 12 also obtained the high curved characteristic more than 1,000,000 times.And on the other hand, for embodiment 9 ~ 12, all obtained the more excellent curved characteristic more than 2,000,000 times.

Table 11

From the above, if the diffraction peak intensity of each crystal face than in the specialized range, then for the rolled copper foil that has added the different interpolation material as Ag and B, also can obtain excellent curved characteristic.

The inventor's etc. investigation

The secondary orientation of crystal face control to(for) passing through as described above gives the principle of higher curved characteristic 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, and below the explanation inventor etc. is to this investigation.

(1) about giving the principle of higher curved characteristic

Opinion, the opinion of Metallkunde and experiment experience so far that the inventor etc. learn from crystal orientation for the principle that obtains higher curved characteristic by the crystal face of controlling secondary orientation, have carried out following investigation.

As mentioned above, when satisfying above-mentioned formula (2)～(4), { 113} face, { 111} face and { the 133} face becomes the state that accumulation has the processing strain, promotes to comprise from { 022} is towards { the recrystallize that the 002} face changes by related processing strain as the secondary orientation of rolled copper foil.

General crystal face for secondary orientation is even think that ratio also can change hardly under the state behind the final cold rolling process in the manufacturing process that keeps rolled copper foil for after the recrystallization annealing operation.But, according to inventor etc., think: under the state that satisfies above-mentioned formula (2)～(4), { 113} face, { 111} face and { when the 133} face promotes recrystallize, by making these crystal faces itself enter { the 002} face of being grown by recrystallize, and become the 002} face and carry out integrated, thereby further make { 002} face raised growth.

In addition, when satisfying above-mentioned formula (5), as secondary orientation { amount of 002} face is suppressed to less state, and { the 002} face suppress to hinder by above-mentioned each crystal face and promotes recrystallize.

As mentioned above, we can say that { accumulation volume of the processing strain of 002} face is few.Processing should tail off and energy is low, and { the 002} face is compared with other crystal orientation, and is slower by the growth of recrystallize.According to the inventor's etc. investigation, so slow danger that the recrystallize of the crystal orientation that hinders other is arranged.Particularly in that { this disadvantage takes place in the border of the crystal grain of the crystal grain of 002} face and other crystal orientation easily, can consider that { diffraction peak intensity of 002} face compares I by making _{{ 002}}Satisfy above-mentioned formula (5), suppress { the growth obstruction that the 002} face causes.

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

Crystallization is rotated

As mentioned above, rolling the adding of final cold rolling process etc., applied stress under compression and the tensile stress more weak than stress under compression to copper material man-hour.Copper crystal in the copper material that is rolled is owing to the rolling stress that adds man-hour produces to { rotation phenomenon of 022} face, along with the progress of rolling processing, the orientation that is parallel to the crystal face of rolling surface mainly forms as { the rolling texture of 022} face.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. 4 to describe.

Fig. 4 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 crystallization turning direction that is caused by tensile deformation, (b) for showing the antipole point diagram of the crystallization turning direction that is caused by compression set.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 Shanxi, (first) editor Nagasaki one, " texture (collection closes Group Woven) ", ball, clear and on January 20th, 59, Fig. 2 .52 (a) of p96, (c)

As shown in Figure 4, the copper crystal in the copper material when only tensile deformation being arranged towards the 111} face rotates, and when only compression set being arranged towards { the 011} face rotates.In the rolling processing, owing to compress composition and be drawn into the distortion that branch merges, therefore, the crystallization turning direction is so not simple.But, more occupy advantage ground distortion owing to be compressed into proportion by subtraction stretching composition, be rolled processing, therefore, generally speaking take place towards the crystallization of 011} face is rotated, and according to compression composition and stretching components in proportions, and also can some towards { the 111} face rotates.At this moment, because compression composition one side occupies advantage, therefore, towards { crystallization that the 111} face has taken place to rotate also takes place towards { crystallization that the 011} face returns is rotated.In addition, opposite with it, also have towards the crystallization that the 011} face has taken place to rotate, arrived the crystallization of 011} face because of the stretching composition towards { 133} the face, { situation that the 111} face rotates.

So can think: if compression composition and stretching composition are keeping the compression composition in the relation of stretching composition, cause the crystallization rotation in existing mixing, then finally become the distribution of the crystal face in main orientation shown in the antipole point diagram of Fig. 5 and secondary orientation.Can think: because compression composition＞stretching composition, therefore, the crystal face in final main orientation be the 011} face, in addition, by the result that compression composition and the crystallization that produces mixing of stretching composition are rotated, the crystal face in secondary orientation is { 113} face, { 111} face, { 133} face, { 001} face.

, be shown as the crystal face that only is distributed with above-mentioned particular orientation among Fig. 5 here, 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 are not all to be odd number value or all to be even number value, does not then occur as diffraction peak.If h, k, l are odd number value and the existence that mixes of even number value, then according to extinction rule, diffraction peak disappears, and can not measure.Therefore, when showing the formation of the rolled copper foil that above-mentioned embodiment etc. is related, by { 113} face, { 111} face and { the 133} face, { 001} face ({ 002} face) is stipulated 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 from the foregoing, 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.Specifically, the compression composition is more big, and is more easy of { the 002} face, { the 113} face, the stretching composition is more big, and is more easy of { 111} face, { 133} face.The crystal face in main secondary orientation is { 002} face, { 113} face, { 111} face and { the 133} face is that { the above-mentioned crystal face of 022} face remains in the copper material because fail to turn to fully, by the adjustment of the compression composition in the final cold rolling process and stretching composition, 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.When adjusting all control parameter of control compression composition and stretching composition, as above-mentioned embodiment, embodiment attempt, 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.Thus, the rotation path of crystallization is that { the 002} face, { the 113} face is towards { the 022} face rotates.

And on the other hand, also having with stress under compression＞tensile stress is prerequisite, makes the copper material attenuation improve the method for degree of finish by increasing the stretching composition.Owing to increased the stretching composition, therefore, the rotation path of crystallization is that { the 111} face, { the 133} face is 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 way of crystallization resulting and arrived for the time being by the compression composition that { crystallization 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.

In addition, it should be noted here that only utilize each composition (stress under compression and tensile stress), material shape can not be processed equably, rolling can not carrying out.That is, by stress under compression and tensile stress the two, when making the thickness attenuation of material, controlled material shape.

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.Can make up these control elementss variedly, the position of neutral point is changed.

The position of related neutrality 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) is calculated roll speed and roller conditional equilibrium directly, that is, and and the position of the neutrality point on the contact surface of the rolling roller that adds man-hour and copper material.In addition, for the detailed content of neutrality point, with reference to following technical literature (second).

(second) Japanese plastic working association volume, " Technology of Plastic Processing series 7 plates are rolling ", Corona company, p14, p27 formula (3.3), p28

Parameter when above-mentioned formula (C) is calculated is above-mentioned control elements, but in these key elements, can consider polytype control method by key element how to select to fix and variable key element.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 the formation of the roller of the combining and configuring of the sum of the hop count of roller, roller, roller, each roller footpath, material, condition of surface (surfaceness) etc. etc., producing different to the applying method of the stress under compression of copper material, frictional coefficient etc.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, it is for possessing major surfaces, and after having a final cold rolling process with a plurality of crystal faces of described major surfaces in parallel, the rolled copper foil before the recrystallization annealing operation,

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

Will by the X-ray diffraction that described major surfaces has been used 2 θ/θ method measure obtain and be that 100 mode converts the diffraction peak intensity of described each crystal face of obtaining than being made as I respectively with aggregate value _{{ 022}}, I _{{ 113}}, I _{{ 111}}, I _{{ 133}}And I _{{ 002}},

Will by about have the 022} face, the 113} face, the 111} face, the 133} 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 002} face or the ICDD card obtained, be that the diffraction peak intensity of 100 described each crystal face that converted compares and is made as I respectively with aggregate value _0{022}, I _0{113}, I _0{111}, I _0{133}And I _0{002}The time,

I _{022}/I _0{022}≥7.0、

I _{113}/I _0{113}≥0.40、

I _{{ 111}}/ I _0{111}〉=0.090 and

I _{133}/I _0{133}≥1.4。

2. rolled copper foil according to claim 1 is characterized in that, I _{{ 002}}/ I _0{002}≤ 0.25.

3. rolled copper foil according to claim 1 and 2 is characterized in that, with the tough pitch copper stipulated among the oxygen free copper stipulated among the JIS C1020 or the JIS C1100 as principal constituent.

4. according to each described rolled copper foil in the claim 1～3, it is characterized in that, added in silver, boron, titanium, the tin at least any.

5. according to each described rolled copper foil in the claim 1～4, it is characterized in that, is described final cold rolling process more than 90% by total degree of finish, and thickness is become below the 20 μ m.

6. according to each described rolled copper foil in the claim 1～5, it is characterized in that, be used for flexible printing patch panel.