CN104109888A - Rolled copper foil with copper plated layer - Google Patents

Abstract

The invention provides a rolled copper foil with a copper plated layer. Even if a copper plated layer is formed, the rolled copper foil still has excellent bending resistance after a recrystallization annealing step. The rolled copper foil with the copper plated layer has a rolled copper foil that is subjected to a step after final cold rolling and then a step before crystallization annealing, and also has a copper plated layer formed on the surface of at least one side of the rolled copper foil. Among multiple crystallization surfaces of the rolled copper foil and the copper plated layer, when the intensity values of diffraction peaks of {111}surfaces, {002}surfaces and {022}surfaces, obtained through X-ray diffraction according to a 2[theta]/]theta] method, are set to be PR{111}, PR{002}, PR{022}, PM{111}, PM{002} and PM{022} respectively, at least any state of the following states is achieved: PM{111}>=15.0 is met, and PM{111}>(PR{111}+5), PM{002}<(PR{002}-10) or PM{002}>(PR{002}+10), PM{022}<(PR{022}-10) or PM{022}>(PR{022}+10) are further met.

Description

Rolled copper foil with copper coating

Technical field

The present invention relates to the rolled copper foil with copper coating, particularly relate to the rolled copper foil with copper coating for flexible printing wiring board.

Background technology

Thin and the flexible excellence of flexible printing wiring board (FPC:Flexible Printed Circuit), thereby the degree of freedom under the actual installation state of electronics etc. is high.Therefore, FPC, except the first-class moving portion of the bend for fold type portable telephone, digital camera, printer, is also widely used in the wiring etc. of the moving portion of the disk relevant devices such as hard disk drive (HDD:Hard Disk Drive), digital multi-purpose CD (DVD:Digital Versatile Disk), CD (CD:Compact Disk).Therefore,, for FPC, as the rolled copper foil of its wiring material, require high curved characteristic, i.e. the excellent resistance to bend(ing) of resistance to alternating bending.

FPC with rolled copper foil via manufacturing such as hot rolling, the operation such as cold rolling.In the manufacturing process of FPC thereafter, utilize heating etc., rolled copper foil is by caking agent or directly fit with the FPC basement membrane (base material) of the resin formation such as polyimide.Rolled copper foil on base material is implemented to the surface working such as etching and made wiring.With rolling and solidify cold rolling after the state of hard compare, the resistance to bend(ing) of the rolled copper foil by the state after the annealing of recrystallization softening significantly improves.Therefore, for example, in the manufacturing process of above-mentioned FPC, use the rolled copper foil having solidified after cold rolling, when avoiding the distortion such as elongation, fold, block rolled copper foil, overlapping on base material.Afterwards, by also holding concurrently as making the closely sealed and compound operation of rolled copper foil and base material and heating, thereby be rolled the recrystallization annealing of Copper Foil, realize the raising of resistance to bend(ing).

Take the manufacturing process of above-mentioned FPC is prerequisite, up to now, the rolled copper foil of resistance to bend(ing) excellence, its manufacture method has been carried out to various research.According to its result, the surface of having reported in a large number rolled copper foil be cubes orientation { 002} face ({ 200} face) reaches all the more that resistance to bend(ing) is higher.

For example, in patent documentation 1, in the median size of recrystallize grain, become and under the condition of 5 μ m～20 μ m, be about to final annealing before cold rolling.In addition, final rolling degree of finish in cold rolling is made as more than 90%.By like this, obtain following cubes set tissue: carry out modified to become under the state of recrystallized structure, by rolling surface by X-ray diffraction, try to achieve the intensity of 200} face be made as I, by micropowder copper by X-ray diffraction, try to achieve { intensity of 200} face is made as I ₀time, I/I ₀>20.

In addition, for example, in patent documentation 2, improve the flourishing degree of final cubes set tissue before cold rolling, the degree of finish in finally cold rolling is made as more than 93%.By further enforcement recrystallization annealing, { integrated intensity of 200} face is I/I in acquisition ₀rolled copper foil>=40, the remarkable prosperity of cubes set tissue.

In addition, for example, in patent documentation 3, the total degree of finish in final cold rolling process is made as more than 94%, and the degree of finish of each rolling is controlled to 15%～50%.By like this, after recrystallization annealing, obtain the grain orientation state of regulation.That is, utilize X-ray diffraction pole graph measure and the rolling surface that obtains { 111} face is with respect to { in the face of 200} face, orientation degree △ β is below 10 °.In addition, in rolling surface as cubes set tissue the standardized diffraction peak intensity [a] of 200} face with { ratio of the standardized diffraction peak intensity [b] of the crystal region in twin crystal relation of 200} face is [a]/[b] >=3.

Like this, in prior art, by improving total degree of finish of final cold rolling process, after recrystallization annealing operation, make the cubes set tissue of rolled copper foil flourishing, thereby realize the raising of resistance to bend(ing).

In addition,, in the rolled copper foil of FPC purposes, in order to improve the laminating intensity with base material, for example, sometimes make it adhere to alligatoring grain.In addition in this case, for example most as patent documentation 4,5, for alligatoring grain is adhered to equably, thereby at the one or both sides formation copper coating of rolled copper foil, realize surperficial smoothing in advance, and then adhere to alligatoring grain.

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

Patent documentation 4: TOHKEMY 2005-340635 communique

Patent documentation 5: TOHKEMY 2010-037585 communique

Summary of the invention

Invent problem to be solved

Yet, be formed with in the rolled copper foil with copper coating of copper coating, even for example use the technology of above-mentioned patent documentation 1～3 to improve the rolled copper foil of resistance to bend(ing), due to alternating bending, also how can there is visible repeated stress failure.That is, with mostly seeing the deterioration of resistance to bend(ing) in the rolled copper foil of copper coating.

The object of the invention is to, even if a kind of copper coating that formed is provided, after recrystallization annealing operation, also can there is the rolled copper foil with copper coating of excellent resistance to bend(ing).

For solving the method for problem

According to the 1st mode of the present invention, a kind of rolled copper foil with copper coating is provided,

It possesses: major surfaces or the back side have after the final cold rolling process of parallel a plurality of crystal planes, the rolled copper foil before recrystallization annealing operation, with be formed on the major surfaces of aforementioned rolled copper foil or the face of at least one side in its back side, major surfaces or become the copper coating with the back side at the interface of aforementioned rolled copper foil with parallel a plurality of crystal planes

In aforementioned a plurality of crystal planes of aforementioned rolled copper foil, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _r{ 111}, I _r{ 002}, I _r022}, by the mark P of the intensity level of each aforementioned diffraction peak _r{ 111}, P _r{ 002}, P _r022} is made as:

P _R{111}=[I _R{111}/(I _R{111}+I _R{002}+I _R{022})]×100、

P _R{002}=[I _R{002}/(I _R{111}+I _R{002}+I _R{022})]×100、

P _R{022}=[I _R{022}/(I _R{111}+I _R{002}+I _R{022})]×100，

In aforementioned a plurality of crystal planes of aforementioned copper coating, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _m{ 111}, I _m{ 002}, I _m022}, by the mark P of the intensity level of each aforementioned diffraction peak _m{ 111}, P _m{ 002}, P _m022} is made as:

P _M{111}=[I _M{111}/(I _M{111}+I _M{002}+I _M{022})]×100、

P _M{002}=[I _M{002}/(I _M{111}+I _M{002}+I _M{022})]×100、

P _M{022}=[I _M{022}/(I _M{111}+I _M{002}+I _M{022})]×100

Time,

Become at least arbitrary state in following state:

Meet following formula (1)

P _M{111}≥15.0…（1），

Further meet following formula (2)

P _m{ 111}>(P _r111}+5) ... (2) state;

Meet following formula (3), (4)

P _M{002}<（P _R{002}-10）…（3）

P _M{002}>（P _R{002}+10）…（4）

In any state;

Meet following formula (5), (6)

P _M{022}<（P _R{022}-10）…（5）

P _M{022}>（P _R{022}+10）…（6）

In any state.

According to the 2nd mode of the present invention, the rolled copper foil with copper coating described in the 1st mode is provided, its meet in following formula (2), (4), (6) at least any:

P _M{111}>（P _R{111}+5）…（2）

P _M{002}>（P _R{002}+10）…（4）

P _M{022}>（P _R{022}+10）…（6）。

According to the 3rd mode of the present invention, the rolled copper foil with copper coating described in the 1st or the 2nd mode is provided,

Aforementioned rolled copper foil is formed by following substances: the fine copper being formed by tough pitch copper or oxygen free copper or the lower concentration copper alloy that tough pitch copper or oxygen free copper is parent phase of take,

Aforementioned rolled copper foil is taked the form of fine copper type set tissue.

According to the 4th mode of the present invention, the rolled copper foil with copper coating described in the 1st～3rd mode is provided,

The whole thickness of aforementioned copper coating and aforementioned rolled copper foil is below the above 20 μ m of 1 μ m,

The thickness of aforementioned copper coating is below the above 1.0 μ m of 0.1 μ m.

According to the 5th mode of the present invention, the rolled copper foil with copper coating described in any one in the 1st～4th mode is provided, it is the rolled copper foil with copper coating for flexible printing wiring board.

Invention effect

According to the present invention, even if provide, formed copper coating, after recrystallization annealing operation, also can there is the rolled copper foil with copper coating of excellent resistance to bend(ing).

Accompanying drawing explanation

Fig. 1 means the schema of the manufacturing process of the rolled copper foil with copper coating that an embodiment of the invention relate to.

The mensuration figure of the X-ray diffraction that Fig. 2 is the use that relates to of embodiments of the invention carries out according to 2 θ/θ method in the rolled copper foil of tough pitch copper.

The mensuration figure of the X-ray diffraction that Fig. 3 is the use that relates to of embodiments of the invention carries out according to 2 θ/θ method in the rolled copper foil of oxygen free copper.

Fig. 4 is the use that relates to of embodiments of the invention is added with the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method in the rolled copper foil of tough pitch copper of Ag.

Fig. 5 is the use that relates to of embodiments of the invention is added with the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method in the rolled copper foil of oxygen free copper of Sn.

Fig. 6 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 1.

Fig. 7 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 2.

Fig. 8 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 3.

Fig. 9 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 4.

Figure 10 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 5.

Figure 11 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 6.

Figure 12 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 7.

Figure 13 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of embodiments of the invention 8.

Figure 14 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of comparative example 1.

Figure 15 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of comparative example 2.

Figure 16 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of comparative example 3.

Figure 17 is the mensuration figure of the X-ray diffraction carrying out according to 2 θ/θ method of comparative example 4.

Figure 18 is the schematic diagram of the slip bend test device measured of the resistance to bend(ing) of the rolled copper foil with copper coating that embodiments of the invention and comparative example are related to.

Figure 19 means the thickness of rolled copper foil of embodiments of the invention and the chart of the relation of bend fracture number of times.

Accompanying drawing explanation:

10: slip bend test device; 11: sample retaining plate; 12: screw; 13: vibration transmission portion; 14: vibration driving body; 50: coupons.

Embodiment

The opinion > that the < inventor etc. obtains

As mentioned above, be formed with in the rolled copper foil of copper coating, even for the such raising of above-mentioned patent documentation 1～3 { ratio of 002} face, thering is the rolled copper foil of excellent resistance to bend(ing), sometimes also can see the deterioration that the resistances to bend(ing) such as repeated stress failure occur after heating.

The inventor etc. find out, such fracture be take copper coating and occurred as starting point.The fracture occurring in copper coating is directly propagated to rolled copper foil, just with the rolled copper foil of copper coating on the whole, is considered to the reason that resistance to bend(ing) is worsened.

The result of the further investigations such as the inventor shows, the rolled copper foil from heating recrystallize by regulation with excellent resistance to bend(ing) is different, and copper coating hardly can be due to heating now and recrystallize.That is, think that the crystalline structure while forming by plating in copper coating maintains the original state residual substantially.Therefore,, at the beginning of being desirably in the formation of copper coating, copper coating has the crystalline structure that possesses sufficient resistance to bend(ing).

Therefore, the inventor etc. are research repeatedly further, thereby expect, makes the crystalline structure of the copper coating at the beginning of forming different from existing copper coating, improves the whole resistance to bend(ing) with the rolled copper foil of copper coating.In addition, the inventor waits the method for also having found to form the copper coating with such crystalline structure.

The present invention be take the above-mentioned opinion of the discoveries such as contriver as basis propose.

< an embodiment of the invention >

(1) with the formation of the rolled copper foil of copper coating

The formation of the rolled copper foil with copper coating first, an embodiment of the invention being related to describes.

The rolled copper foil with copper coating that present embodiment relates to possess by oxygen free copper, tough pitch copper or the face of at least one side of take rolled copper foil that lower concentration copper alloy that oxygen free copper, tough pitch copper is parent phase forms and being formed at rolled copper foil on copper coating.In addition,, about the described rolled copper foil with copper coating, in order for example to use in the purposes of the flexible printed material as FPC, the whole thickness mode below 20 μ m more than 1 μ m of take forms.In addition, wherein, the thickness mode below 1.0 μ m more than 0.1 μ m of copper coating of take forms.

(summary of rolled copper foil)

The rolled copper foil possessing with the rolled copper foil of copper coating is configured to for example possesses tabular as the rolling surface of major surfaces, and rolling surface or the back side have parallel a plurality of crystal planes.This rolled copper foil be such as for take oxygen free copper (OFC:Oxygen-Free Copper) thereby, the fine copper such as tough pitch copper implements hot-rolled process described later, cold rolling process etc. as raw-material ingot bar and makes the rolled copper foil after cold rolling process specific thickness, final, before recrystallization annealing operation.That is, the rolled copper foil that present embodiment relates to be by for example total degree of finish be more than 90%, be preferably more than 94%, more than 96% final cold rolling process more preferably, to comprise that the mode that the whole thickness of copper coating becomes routine thickness described above forms.Then, as mentioned above, if for example held concurrently, for the operation of the base material laminating with FPC, the rolled copper foil with copper coating is implemented to recrystallization annealing operation, can expect by modified rolled copper foil, to be there is excellent resistance to bend(ing) in recrystallize.

As the raw-material oxygen free copper of rolled copper foil, be that purity such as defineds such as JIS C1020 is more than 99.96% copper material.Oxygen level can be not exclusively zero, for example, can contain the oxygen of several ppm left and right.In addition as the raw-material tough pitch copper of rolled copper foil, be that purity such as defineds such as JIS C1100 is more than 99.9% copper material.In the situation of tough pitch copper, oxygen level is for example 100ppm～600ppm left and right.The rolled copper foil being formed by these starting material is preferably taked for example form of fine copper type set tissue (also referred to as proof gold genotype set tissue).Or, as rolled copper foil, also can use the interpolation material that indium addition tin (Sn), silver (Ag), boron (B), titanium (Ti) etc. are stipulated in oxygen free copper, tough pitch copper, make lower concentration copper alloy, thereby adjusted the starting material of every characteristics such as thermotolerance.Now, the addition of interpolation material is preferably made as and can not hinders the scope that is formed the crystalline orientation form of fine copper type set tissue by the fine copper of parent phase.

About total degree of finish of rolled copper foil in final cold rolling process, if the thickness of the workpiece before final cold rolling process (copper coin material) is made as to T _b, the thickness of the workpiece after final cold rolling process is made as to T _a, be expressed as total degree of finish (%)=[(T _b-T _a)/T _b] * 100.By total degree of finish is located in above-mentioned scope, in recrystallization annealing operation after heating { ratio of 002} face raises, and can obtain the rolled copper foil with high resistance to bend(ing).

(summary of copper coating)

The copper coating possessing with the rolled copper foil of copper coating is to form on the rolling surface of the major surfaces as rolled copper foil or the face of at least one side in its back side such as using to electroplate to wait.About copper coating, for example outmost major surfaces or the conduct at the rolled copper foil as with copper coating has parallel a plurality of crystal planes with the back side at the interface of rolled copper foil.The copper coating that present embodiment relates to forms for example thin than rolled copper foil, for example, be configured to the thickness below the above 1.0 μ m of 0.01 μ m.

By forming such thickness, for example utilize the flattening surface that makes rolled copper foil as the copper coating of the substrate of alligatoring grain described later, rustproof layer, can make alligatoring grain adhere to equably or rustproof layer is formed uniformly.In addition, thinner than rolled copper foil by making by this way copper coating form, easily realize the raising with the rolled copper foil of copper coating resistance to bend(ing) as a whole.In present embodiment, in order not produce the impact in practical application, using the thickness of 1.0 μ m as higher limit, copper coating forms to obtain Bao Yuehao more.

(crystalline structure of copper coating)

A plurality of crystal planes of the copper coating possessing with the rolled copper foil of copper coating have the state of regulation with respect to a plurality of crystal planes of above-mentioned rolled copper foil.Such state can be used by the diffraction peak of the X-ray diffraction acquisition of carrying out according to 2 θ/θ method, identify as follows.

That is, among a plurality of crystal planes of rolled copper foil, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _r{ 111}, I _r{ 002}, I _r{ 022}.In addition, the mark of the intensity level of each diffraction peak is made as to P _r{ 111}, P _r{ 002}, P _r{ 022}.

The mark of the intensity level of each diffraction peak is represented by following formula:

P _R{111}=[I _R{111}/(I _R{111}+I _R{002}+I _R{022})]×100，

P _R{002}=[I _R{002}/(I _R{111}+I _R{002}+I _R{022})]×100，

P _R{022}=[I _R{022}/(I _R{111}+I _R{002}+I _R{022})]×100。

In addition, in a plurality of crystal planes of copper coating, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _m{ 111}, I _m{ 002}, I _m{ 022}.In addition, the mark of the intensity level of each diffraction peak is made as to P _m{ 111}, P _m{ 002}, P _m{ 022}.

The mark of the intensity level of each diffraction peak is represented by following formula:

P _M{111}=[I _M{111}/(I _M{111}+I _M{002}+I _M{022})]×100，

P _M{002}=[I _M{002}/(I _M{111}+I _M{002}+I _M{022})]×100，

P _M{022}=[I _M{022}/(I _M{111}+I _M{002}+I _M{022})]×100。

Now, copper coating has the crystalline structure that meets following formula (1),

P _M{111}≥15.0…（1）。

Further, copper coating has the crystalline structure that becomes at least arbitrary state in following state:

Meet following formula (2)

P _m{ 111}>(P _r111}+5) ... (2) state;

Meet following formula (3), (4)

P _M{002}<（P _R{002}-10）…（3）

P _M{002}>（P _R{002}+10）…（4）

In any state;

Meet following formula (5), (6)

P _M{022}<（P _R{022}-10）…（5）

P _M{022}>（P _R{022}+10）…（6）

In any state.

In addition, preferably copper coating has and meets above-mentioned formula (2), (4), (6),

P _M{111}>（P _R{111}+5）…（2）

P _M{002}>（P _R{002}+10）…（4）

P _M{022}>（P _R{022}+10）…（6）

In at least crystalline structure of any.

The meaning that below copper coating is had to above such crystalline structure describes.

(effect of crystalline structure)

As mentioned above, after recrystallization annealing operation, { ratio of 002} face raises, has excellent resistance to bend(ing) to the rolled copper foil in present embodiment.

On the other hand, under the state of the crystalline structure of copper coating after final cold rolling process, before recrystallization annealing operation, meet above-mentioned formula (1), further meet at least arbitrary state in formula (2), (3) or (4), (5) or (6).By like this, no matter copper coating, in the front and back of recrystallization annealing operation, all can obtain excellent resistance to bend(ing).

No matter copper coating how, generally speaking, by electroplating during form layers, be easily subject to the rheotaxial growth of impact of the crystalline orientation of substrate.Can think, for example, in the existing rolled copper foil with copper coating, copper coating is easily subject to, as the impact of the crystalline orientation of the rolled copper foil of substrate, rheotaxial growth occurs, and is easy to become the crystalline orientation same with the crystalline orientation of rolled copper foil.As described later, copper coating forms for the rolled copper foil after final cold rolling process for example, before recrystallization annealing operation.Now, the crystalline orientation of rolled copper foil becomes the crystalline orientation state of rolling set tissue.Therefore, copper coating also should become the state same with the crystalline orientation of rolling set tissue.

At the rolled copper foil with copper coating to such, heat, while rolled copper foil being softened by recrystallize, the crystalline orientation of the rolling set tissue of rolled copper foil changes to the crystalline orientation of recrystallize set tissue, thereby rolled copper foil has obtained excellent resistance to bend(ing).Yet as mentioned above, according to inventor's etc. discovery, by such heating, copper coating hardly can recrystallize.

During recrystallization annealing operation, the motivating force of the variation of the crystalline orientation of rolled copper foil is: the processing strain of the savings being caused by rolling processing in final cold rolling process in rolled copper foil and the heat energy being produced by the heating of recrystallization annealing.Yet, even if the crystalline orientation of copper coating is changed, now can be used as the heat energy also only serving as reasons and heating and produce of motivating force.Therefore can think, in copper coating, because motivating force is not enough, the variation of crystalline orientation occur hardly, keep the crystalline orientation state of rolling set tissue that epitaxially grown state has occurred.Due to such crystalline orientation, in copper coating, can not obtain sufficient resistance to bend(ing).

Therefore, the inventor etc. are for when forming copper coating, and the crystalline structure of copper coating does not at least become the crystalline orientation state of rolling set tissue and conducts in-depth research.Its result shows, if under the state with the rolled copper foil of copper coating after final cold rolling process, before recrystallization annealing operation, there is the crystalline structure that meets above-mentioned formula (1), further meets at least arbitrary state in formula (2), (3) or (4), (5) or (6), form the copper coating of resistance to bend(ing) excellence.

The detailed mechanism that shows high resistance to bend(ing) about such copper coating also in further investigation, but can say, by meeting regulation formula as described above, at least the crystalline structure of copper coating does not become extension state.

That is,, if the rolling set tissue of the rolled copper foil that present embodiment is related to carries out the X-ray diffraction carrying out according to 2 θ/θ method, { 022} face shows as main peak.Then the, { intensity of diffraction peak performance the last 2 of 002} face.On the other hand, { the diffraction peak intensity value of 111} face is minimum.

Therefore, the inventor etc. pay close attention to { 111} face, { 002} face, { diffraction peak of these 3 faces of 022} face, the mark P to each diffraction peak intensity value _r{ 111}, P _r{ 002}, P _r{ the mark P of the diffraction peak intensity value of 022} and the copper coating corresponding with them _m{ 111}, P _m{ 002}, P _m{ 022} compares.By like this, can judge whether the state of rolled copper foil and the crystalline orientation of copper coating is identical.

That is, in the rolled copper foil that present embodiment relates to, { the mark P of the diffraction peak intensity value of 111} face for example _r{ 111} should be minimum.But, by meeting formula (1), { the mark P of the diffraction peak intensity value of 111} face of the related copper coating of present embodiment _m{ 111} is minimum mark not like that, shows to keep the mark of regulation and { 111} face exists in the crystalline structure of copper coating.

In addition, can also say in addition, if copper coating has at least crystalline structure of any meeting in formula (2), (3) or (4), (5) or (6), can not become extension state, and become the state different from the crystalline orientation of rolled copper foil.

That is, formula (2) meaning is the P of copper coating _m{ the P of 111} and rolled copper foil _r{ 111} compares fully large, shows that the crystalline orientation state of copper coating is different from rolled copper foil.

In addition, formula (3) meaning is the P of copper coating _m{ the P of 002} and rolled copper foil _r{ 002} compares minimum.In addition, formula (4) meaning is the P of copper coating _m{ the P of 002} and rolled copper foil _r{ 002} compares greatly.Like this, formula (3), (4) all represent the P of copper coating _m{ the P of 002} and rolled copper foil _r{ 002} is different.

In addition, formula (5) meaning is the P of copper coating _m{ the P of 022} and rolled copper foil _r{ 022} compares minimum.In addition, formula (6) meaning is the P of copper coating _m{ the P of 022} and rolled copper foil _r{ 022} compares greatly.Like this, formula (5), (6) all represent the P of copper coating _m{ the P of 022} and rolled copper foil _r{ 022} is different.

If as described above,, copper coating meets the arbitrary state in above-mentioned formula (2), (3) or (4), (5) or (6), can say that epitaxy does not occur the crystalline orientation state of copper coating, different from rolled copper foil.Now, can not also 1 that only meets in the state of formula (2), (3) or (4), (5) or (6), but meet a plurality of states.

In addition can say preferably by copper coating meet in above-mentioned formula (2), (4), (6) at least any, the crystalline structure of copper coating is not only different from rolled copper foil, also becomes the higher crystalline structure of easy acquisition resistance to bend(ing).Also in further investigation, known at least by { 002} face exists in a large number, and the resistance to bend(ing) of the copper materials such as rolled copper foil improves about the meaning that meets above-mentioned various (2), (4), (6).Therefore infer, for example, by meeting formula (4), the resistance to bend(ing) of copper coating also improves.

In addition, on the other hand, at copper coating, do not meet any state in above-mentioned formula (1) or above-mentioned formula (2), (3) or (4), (5) or (6) all in ungratified situation, there is epitaxy with respect to the crystalline orientation of rolled copper foil in the crystalline orientation state that can say copper coating, roughly equal with rolled copper foil.

(with other of the rolled copper foil of copper coating, forming)

On the copper coating of the rolled copper foil with copper coating, for example alligatoring copper coating, capsule copper coating, rustproof layer can be arranged according to said sequence.Alligatoring copper coating has alligatoring grain.Alligatoring grain is such as copper (Cu) simple substance or in copper, contains the metallics more than at least a kind, diameter 1 μ m left and right in iron (Fe), molybdenum (Mo), nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn) etc.Capsule copper coating is that alligatoring grain is grown to strumae, so-called packing coating.Rustproof layer has the stepped construction that for example nickel coating, zinc coating, 3 valency chromate treating layers, silane coupled layer form according to said sequence.

(2) with the manufacture method of the rolled copper foil of copper coating

The copper coating relating in order to obtain present embodiment, the inventor etc. for final cold rolling process after, the rolled copper foil before recrystallization annealing operation become the crystalline orientation different from having there is epitaxially grown crystalline orientation state, organize the state of different crystalline orientations with rolling set, conduct in-depth research.

Particularly, think and can in the plating bath when forming copper coating, add the medicament (below also referred to as epitaxy inhibitor, p-nJie Erjiguan non-epitaxial p-n junction diode agent) that can suppress, so that copper coating can epitaxy with respect to rolled copper foil, and attempted various additives.Its results verification works as the epitaxially grown p-nJie Erjiguan non-epitaxial p-n junction diode agent that suppresses copper coating to the additive of the regulation used such as electroplating.Particularly, find in the additive of the regulation used as gloss-imparting agent up to now, as the new effect of p-nJie Erjiguan non-epitaxial p-n junction diode agent.

Then,, based on above opinion, the manufacture method of the rolled copper foil with copper coating an embodiment of the invention being related to Fig. 1 describes.Fig. 1 means the schema of the manufacturing process of the rolled copper foil with copper coating that present embodiment relates to.

(the preparatory process S10 of ingot bar)

As shown in Figure 1, first manufacture the rolled copper foil part with the rolled copper foil of copper coating.

That is, the fine copper such as oxygen free copper (OFC), tough pitch copper of take are cast as starting material, thereby prepare ingot bar (ingot casting).Ingot bar forms for example has the tabular of specific thickness, Rack.As raw-material oxygen free copper, tough pitch copper, also can make the lower concentration copper alloy that is added with the interpolation material of regulation in order to adjust the various features of rolled copper foil.

The various features of the rolled copper foil that can adjust with interpolation material for example has thermotolerance.As mentioned above, in the rolled copper foil of using at FPC, for obtaining the recrystallization annealing operation of high resistance to bend(ing), hold concurrently as for example carrying out with the operation of the base material laminating of FPC.Heating temperature during laminating is set according to the solidification value of the solidification value of the base material being formed by resin etc. such as FPC, the caking agent that uses etc., and the wide ranges of temperature condition is varied.In order to make the softening temperature of rolled copper foil be applicable to the Heating temperature of setting like this, suitable interpolation can be adjusted the stable on heating interpolation material of rolled copper foil sometimes.

The ingot bar using as present embodiment, by add not adding the ingot bar of material, the ingot bar that is added with the interpolation material of several types is illustrated in following table 1.Here, in the scope of the addition of the interpolation material shown in table 1, the state of the crystalline orientation of rolled copper foil is all taked the form of fine copper type set tissue.

[table 1]

In addition, as the interpolation material shown in table 1, other add material, in the typical example of the interpolation material that makes thermotolerance increase or decline, for example, there is the example of appointing one or more elements in the tin (Sn) of interpolation 10ppm～2000ppm left and right, silver-colored (Ag), boron (B), niobium (Nb), titanium (Ti), nickel (Ni), zirconium (Zr), vanadium (V), manganese (Mn), hafnium (Hf), tantalum (Ta) and calcium (Ca).Or, have add Ag as the 1st adding element, add and appoint one or more elements as the 2nd example that adds element in above-mentioned element.In addition, all right indium addition chromium (Cr), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), gold (Au) etc.

Here, the composition of ingot bar is also substantially remained stationary in the rolled copper foil after final cold rolling process S40 described later, has added the in the situation that of adding material in ingot bar, and ingot bar forms substantially identical interpolation material concentration with rolled copper foil.

In addition, the temperature condition in annealing operation S32 described later suitably changes according to the thermotolerance being determined by copper material, interpolation material.But, above-mentioned copper material, add material, the change of the temperature condition of the annealing operation S32 that carries out according to them etc. exerts an influence hardly to the effect of present embodiment.

(hot-rolled process S20)

Then, the ingot bar of preparing is implemented to hot rolling, the thin sheet material of specific thickness after the casting of manufactured Board thickness rate.

(repeating operation S30)

Then, repeat to implement the cold rolling process S31 of stipulated number and the repetition operation S30 of annealing operation S32.That is, to implementing above-mentioned sheet material cold rolling and that processing has been solidified, implement anneal, make sheet material annealing, thereby relax processing, solidify.By repeating this operation of stipulated number, be called as the copper bar of " blank ".In copper material, be added with while adjusting stable on heating interpolation material etc., according to the thermotolerance of copper material, suitably change the temperature condition of anneal.

Here, repeat, in operation S30, the annealing operation S32 in repetitive process to be called " process annealing operation ".In addition, by repeat finally, at the annealing operation S32 that is about to carry out carrying out before the final cold rolling process S40 of aftermentioned, be called " final annealing operation " or " blank anneal operation ".In blank anneal operation, above-mentioned copper bar (blank) is implemented to blank anneal and process, obtain the blank of annealing.In blank anneal operation, also according to the suitable changing temperature condition of the thermotolerance of copper material.Now, blank anneal operation is preferably for example, under the temperature condition that can fully relax the processing strain being caused by above-mentioned each operation, processing under substantially equal temperature condition and implementing with Full Annealing.

(final cold rolling process S40)

Then, implement final cold rolling process S40.Final cold rolling to be also referred to as final processing cold rolling, and annealing blank continuous several times is implemented to cold rolling as final processing, makes thin copper foil shape.Now, the total degree of finish in final cold rolling process S40 is made as more than 90%, is preferably made as more than 94%, be more preferably made as more than 96%, to obtain the rolled copper foil with high resistance to bend(ing).By like this, after recrystallization annealing operation, make the rolled copper foil of the excellent resistance to bend(ing) of easy acquisition.

By above operation, manufacture that present embodiment relates to the rolled copper foil in the rolled copper foil of copper coating.

(copper coating forms operation S50)

Then, on the rolling surface of rolled copper foil or the face of at least one side in its back side, form copper coating.

While forming copper coating, by rolled copper foil successively dipping in degreasing bath, acid elution are bathed, the surface of rolled copper foil is washed in advance.That is,, in degreasing is bathed, use such as basic solutions such as sodium hydroxide (NaOH) aqueous solution and carry out catholyte degreasing.Then in acid elution is bathed, with for example sulfuric acid (H ₂sO ₄) acidic solution such as the aqueous solution, copper etchant solution implements acid elution to the surface of rolled copper foil, realizes the neutralization of the upper residual basic solution in surface,, the copper oxide film (CuO) forming on surface etc. is removed meanwhile.

The formation of copper coating can be used such as electroplating etc.As plating bath, can use and for example fill with copper sulfate (CuSO ₄) and sulfuric acid (H ₂sO ₄) be the acid copper plating bath such as copper sulfate-sulfuric acid bath of the aqueous solution of main component.Here, from viewpoints such as cost aspects, be made as use copper sulfate-sulfuric acid bath etc., but the operable solution of electroless copper bath etc. are not limited to this.

Now, preferably make electroplating current density less than limit current density.By like this, suppressed lip-deep concavo-convex generation, can obtain more smooth copper coating., productivity raising of electroplating current density height.Therefore, preferably electroplating current density is set on highland in the scope less than limit current density and as far as possible.Following illustration is electroplated the standard of condition.But, following condition is an example of plating condition eventually, is not limited only to this.The liquid composition of copper sulfate-sulfuric acid bath etc., liquid temperature, electrolytic condition can be selected in scope leniently.

Copper sulfate pentahydrate: 20g/L～300g/L

Sulfuric acid: 10g/L～200g/L

Liquid temperature: 15 ℃～50 ℃

Electroplating current density: 1A/dm ²～30A/dm ²(being less than limit current density)

Electroplating time: 1 second～60 seconds

In addition,, in copper sulfate-sulfuric acid bath, as additive, add the compound that such as two (3-sulfopropyl) two sulphur disodiums (below also referred to as SPS), 3-sulfydryl-1-propanesulfonic acid (below also referred to as MPS) etc. has sulfydryl (SH).In addition,, as other additives, adding is liquid and the flow agent of main component with polyoxyethylene glycol (PEG, Poly Ethylene Glycol).

In the acid copper-plating that has added such additive is bathed, the rolled copper foil cleaning has been carried out on dipping surface, and the electroplating processes that to implement to take rolled copper foil be negative electrode forms copper coating at the one or both sides of rolled copper foil.By like this, for the rolled copper foil after final cold rolling process, before recrystallization annealing operation, form the crystalline orientation different from having there is epitaxially grown crystalline orientation state, organize the state of different crystalline orientations with rolling set, thereby obtain the copper coating that present embodiment relates to.That is, as epitaxy inhibitor, (p-nJie Erjiguan non-epitaxial p-n junction diode agent) plays a role the compositions such as SPS, MPS in such liquid.

Conventionally, take liquid that SPS, MPS etc. are main component is used as gloss-imparting agent and plays a role in copper plating treatment.In this case, about described liquid, conventionally for every 1 liter of electroplate liquid, if SPS adds to become the mode of 5mg～10mg left and right.

Yet, the discoveries such as the inventor, by adding such as SPS, MPS etc. with the amount more than common amount, for the rolled copper foil after final cold rolling process, before recrystallization annealing operation, can obtain the copper coating of the crystalline orientation different from having there is epitaxially grown crystalline orientation.According to the inventor's etc. discovery, infer when forming copper coating, utilize the p-nJie Erjiguan non-epitaxial p-n junction diode agent such as SPS, MPS of adding with the amount than conventionally many, in copper coating, put aside some energy.Think in addition, this energy has the size of following degree: the copper coating not crystalline orientation ground of influence of rolled Copper Foil carries out crystal growth, is that copper coating is not with respect to rolled copper foil generation epitaxy.

At present, the suppositions such as the inventor, to copper coating, giving such energy may be to occur by following arbitrary effect.That is, on the one hand, think it is mainly a large amount of SPS of interpolation etc. and draw role when being compared to common gloss-imparting agent and using.In addition, on the other hand, except a large amount of interpolation SPS etc., also think some interaction of such SPS etc. and other liquids.As other liquids, can think: the main component of other liquids that add in electroplate liquid or be not the composition of main component or/and be not only liquid, also have some one-tenth of electroplate liquid to grade.

Such effect, purposes, the using method of the SPS that the inventor etc. find etc. are completely different as existing effect, purposes, the using method of gloss-imparting agent from these compounds, are novel effect, purposes, using method.

Above-mentioned viewpoint is also obvious from the alligatoring paper tinsel of for example above-mentioned patent documentation 4,5 and the rolled copper foil with copper coating that above-mentioned present embodiment relates to are compared.

In patent documentation 4,5, for alligatoring knurl is adhered to equably, on the surface of rolled copper foil, formed copper coating.Object is now, by changing current density, seeks the planarization on copper coating surface and the depression that is called as indenture (Crater) that reduces copper coating surface, makes the alligatoring knurl homogenizing forming thereon.In such patent documentation 4,5, for having there is epitaxially grown state to the crystalline orientation of rolled copper foil in copper coating, and this can easily infer by reason below.

First, in patent documentation 4, originally do not use the medicaments such as SPS.In addition about forming other disclosures of the method for copper coating, be all also known content.Can infer thus, copper coating must be that epitaxially grown state has occurred the crystalline orientation to rolled copper foil.

In addition,, in patent documentation 5, for using the embodiment of SPS also disclose, but from the result of described embodiment, supposition remains copper coating, to the crystalline orientation of rolled copper foil, epitaxially grown state has occurred.Particularly, the thickness of the embodiment 1,4 of patent documentation 5 and the copper coating of comparative example 2 is approximately 0.1 μ m.In addition, no matter whether used SPS, all it doesn't matter, and flex life number of times is the result that mutual cardinal principle is identical, is 4.1 * 10 ⁶～4.5 * 10 ⁶inferior.Herein, flex life number of times can be used as one of index of resistance to bend(ing), and resistance to bend(ing) is higher more at most can to say flex life number of times.Like this, even used the copper coating of SPS, also only obtain and the resistance to bend(ing) of not using the copper coating equal extent of SPS, therefore think for there is epitaxially grown state with respect to rolled copper foil.

Like this, in patent documentation 4,5, think, for the resistance to bend(ing) of rolled copper foil monomer, by giving, epitaxially grown copper coating has occurred, can make the resistance to bend(ing) deterioration with the rolled copper foil integral body of copper coating.Here, in the bend fracture number of times that the flex life number of times that patent documentation 4, patent documentation 5 are recorded and embodiments of the invention described later etc. are recorded, the differences such as condition determination such as bending radius during due to Copper Foil bending, thereby can not merely compare.

(surface treatment procedure S60)

The surface of the copper coating forming by above operation is implemented to the processing of regulation, thereby manufacture the rolled copper foil with copper coating that present embodiment relates to.

Herein, as the surface treatment of regulation, as follows, can carry out for example alligatoring copper coating, capsule copper coating, rustproof layer on copper coating, to form successively such processing.But, also can not carry out these processing of following explanation.

First, to form the example of alligatoring copper coating on copper coating, describe.

As the plating bath that forms alligatoring copper coating, can use such as acid copper-platings such as copper sulfate-sulfuric acid baths and bathe.The ion component that also can coordinate in addition, more than a kind iron (Fe), molybdenum (Mo), nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn) etc. in acid copper-plating is bathed.

In addition, in alligatoring copper facing, using copper coating as substrate, with high current density more than limit current density, the i.e. so-called current density of burning plating of formation, carry out electrolysis.But, the liquid composition of now copper sulfate-sulfuric acid bath etc., liquid temperature, electrolytic condition can be selected in scope leniently.By like this, electrodeposit, precipitate are attached on copper coating, and their are hypertrophyization further, thereby obtain for example alligatoring grain about diameter 1 μ m.

Then, to forming the example of capsule copper coating, describe.

That is, utilization is carried out coating plating lower than the electric current of the limit current density of above-mentioned plating bath to the alligatoring grain of alligatoring copper coating, thereby makes alligatoring grain be grown to warty shot copper., when wanting to make alligatoring grain not keep small state, also can not form capsule copper coating.Now, the liquid composition of copper sulfate-sulfuric acid bath etc., liquid temperature, electrolytic condition can be selected in scope leniently.In addition, now also can in plating bath, add organism and add material.

Then, to forming the example of rustproof layer, describe.

Rustproof layer is also referred to as aftertreatment coating, can obtain sufficient rustless property thus.First, form nickel coating or nickel alloy coating, the diffusion of seeking copper suppresses.Then, form zinc coating or zn alloy coating, seek stable on heating raising.Then, use the formation 3 valency chromate treating layers such as response type chromic acid salt liquid of 3 valency chromium types.Afterwards, as chemical treatment tunicle, form for example silane coupled layer, seek the raising with the adaptation of the base material of FPC etc.

By above operation, complete the surface treatment of copper coating.

(3) manufacture method of flexible printing wiring board

Below, the manufacture method of the flexible printing wiring board (FPC) of the rolled copper foil with copper coating that use an embodiment of the invention are related to describes.

(recrystallization annealing operation (CCL operation))

First, the rolled copper foil with copper coating that present embodiment is related to is cut into the size of regulation, fits, thereby form CCL(copper clad laminate (Copper Clad Laminate) with the base material of FPC such as by resin formation such as polyimide).Now, can use by caking agent and fit, form the method for 3 layer material CCL; By caking agent, directly do not fit, any in the method for formation 2 layer material CCL.In the situation that using caking agent, by heat treated, make the caking agents such as above-mentioned silane coupling agent solidify, thereby make with the rolled copper foil of copper coating there is copper coating and be attached to face and the base material of alligatoring grain etc. of copper coating closely sealed and compound.In the situation that not using caking agent, by heating, pressurization, make with the rolled copper foil of copper coating there is copper coating and be attached to face and the base material of alligatoring grain etc. of copper coating directly closely sealed.Heating temperature, time can suitably be selected according to the solidification value of caking agent, base material etc., for example can be made as 150 ℃ of above 400 ℃ of following temperature and 1 minute above below 120 minutes.

The thermotolerance of the rolled copper foil possessing with the rolled copper foil of copper coating as mentioned above, is adjusted according to Heating temperature now.Therefore the rolled copper foil of, processing by final cold rolling process S40 the state having solidified by above-mentioned heating, soften and in recrystallize by modified.That is, on base material, laminating is held concurrently as the recrystallization annealing operation of the rolled copper foil of the rolled copper foil to copper coating with the CCL operation of the rolled copper foil of copper coating.

Like this, by CCL operation, hold concurrently as recrystallization annealing operation, until the rolled copper foil with copper coating is fitted in the operation of base material, the state that the processing of rolled copper foil after final cold rolling process S40 of can take has been solidified, rolled copper foil with copper coating is operated, can make the distortion such as elongation when the rolled copper foil with copper coating is fitted in to base material, fold, bending be difficult to occur.

In addition, the softening of rolled copper foil as described above show by recrystallization annealing operation, the rolled copper foil that obtains modified, has the rolled copper foil of recrystallized structure.Particularly, can obtain { the ratio raising of 002} face, the rolled copper foil of resistance to bend(ing) excellence.

On the other hand, copper coating do not have as rolled copper foil, have the motivating force of the recrystallize such as processing strain.Therefore, from crystallography, consider, such crystalline structure is difficult to change as the rolling Copper Foil.That is, in copper coating, run through the front and back of recrystallization annealing operation, it is substantially certain that its crystalline orientation keeps.Now, the crystalline orientation of copper coating is not that epitaxially grown state has occurred, that is, and not in organizing equal crystalline orientation with rolling set.By like this, copper coating is no matter be before recrystallization annealing operation or all have afterwards excellent resistance to bend(ing).

(surface working operation)

Then, to fitting in the rolled copper foil with copper coating of base material, implement surface working operation.In surface working operation; carry out following operation: thus to the rolled copper foil with copper coating, use the wiring that forms copper wiring etc. such as the method such as etching to form operation; in order to improve copper wiring, implement the surface-treated surface treatment procedures such as electroplating processes with the connection reliability of other electronic units, and the protective membrane that forms the protective membranes such as soldering-resistance layer in the mode of the part in covering copper wiring in order to protect copper wiring etc. forms operation.

By above operation, manufacture the FPC used the rolled copper foil with copper coating that present embodiment relates to.

< other embodiments of the present invention >

Above, embodiments of the present invention are illustrated, but the present invention is not limited to above-mentioned embodiment, within not departing from the scope of its purport, can carries out various changes.

For example, in the above-described embodiment, the interpolation material that the thermotolerance of the rolled copper foil possessing as the rolled copper foil to copper coating is adjusted, is mainly used Sn, Ag etc., but add material, is not limited to the cited materials such as Sn, Ag, above-mentioned typical example.In addition, the every characteristic that can adjust by interpolation material is not limited to thermotolerance, and the various features that can adjust as required suitably selects to add material.

In addition, in the above-described embodiment, the CCL operation in the manufacturing process of FPC is held concurrently as the recrystallization annealing operation for rolled copper foil, but recrystallization annealing operation also can be used as the operation different from CCL operation, carries out.

In addition, in the above-described embodiment, rolled copper foil with copper coating is used to FPC purposes, but is not limited to this with the purposes of the rolled copper foil of copper coating, can also be for the negative pole current collection Copper Foil of for example lithium-ion secondary cell, other need resistance to bend(ing) other purposes.In addition, about the thickness of the rolled copper foil with copper coating, also can be according to the various uses with headed by FPC purposes, be made as ultra-thin below 10 μ m or surpass 20 μ m etc.

In addition, in the above-described embodiment, make copper coating thinner than rolled copper foil, but be not limited to this.Even if make copper coating for example thick than rolled copper foil, also can obtain raising with the regulation effect of the present invention of the resistance to bend(ing) as a whole of the rolled copper foil of copper coating.

In addition, in the above-described embodiment, rolled copper foil is taked the form of fine copper type set tissue, but is not limited to this.For example, inferior for the situation except FPC purposes, also can take the form of alloy-type set tissue.

In addition, in the above-described embodiment, on copper coating, be provided with alligatoring copper coating, capsule copper coating, rustproof layer, but the combination of these layers is arbitrarily.For example, in the situation that making alligatoring grain little, capsule copper coating can be set.In addition, also alligatoring copper coating, capsule copper coating can be set, rustproof layer is directly set on copper coating.In addition, first the purposes according to application with the rolled copper foil of copper coating, that is, in purposes except FPC purposes etc., also can not consider and the adaptation of base material, the formation on copper coating all can also be omitted, and is made as for example coarsening-free.

In addition, in the above-described embodiment, total degree of finish in final cold rolling process S40 is made as to 90% and with first-class, rolled copper foil, obtains excellent resistance to bend(ing), even but the total degree of finish in final cold rolling process is made as and is for example less than 90%, also can obtain independently with it the regulation effect of the copper coating that has improved resistance to bend(ing).Therefore, inferior as long as obtain the situation that resistance to bend(ing) to a certain degree gets final product, force down rolled copper foil total degree of finish, such as being low to moderate, be less than 90% or be less than 80% etc., can reduce the load in manufacturing process.

In addition, in the above-described embodiment, as copper coating, do not form the manufacture method of the rolled copper foil with copper coating of the crystalline structure of rolled copper foil, in the plating etc. of having used the additives such as SPS, MPS, found the effect as the regulation of epitaxy inhibitor (p-nJie Erjiguan non-epitaxial p-n junction diode agent)., the essence of using this SPS, MPS itself not to invent, in addition, also can be used and have other additives that agent is worked as p-nJie Erjiguan non-epitaxial p-n junction diode.Like this, just can fully obtain effect of the present invention.

After all, main points of the present invention are following 2 points: the copper coating with the rolled copper foil of copper coating epitaxy does not occur, do not become the crystalline structure same with rolled copper foil, and copper coating obtains excellent resistance to bend(ing) thus.

Here, in order to realize effect of the present invention, might not need above-mentioned cited whole operations.Above-mentioned embodiment, the cited various conditions of aftermentioned embodiment are also always illustration, can suitably change.

[embodiment]

Below, the embodiment the present invention relates to is described together with comparative example.

(1) with the making of the rolled copper foil of copper coating

The making step of the rolled copper foil with copper coating below embodiment 1～32 and comparative example 1～16 being related to describes.

(making of rolled copper foil)

First make rolled copper foil.Starting material used have 4 kinds: the oxygen free copper that the purity that is added with Sn in the scope that the tough pitch copper that the purity that is added with Ag in the scope that the oxygen free copper that the tough pitch copper that purity is 99.9%, purity are 99.99%, addition are controlled at 180ppm～220ppm is 99.9%, addition are controlled at 30ppm～90ppm is 99.99%.Step and method by same with above-mentioned embodiment, obtains rolled copper foil by these ingot bars.Now, for embodiment and comparative example both sides, all making thickness is the rolled copper foil of 8.0 μ m, 11.0 μ m, 16.5 μ m, 17.0 μ m.In addition, now embodiment is made as consistent with the various manufacturing conditions in comparative example.

Now, the sheet material of the thickness 8mm obtaining in hot-rolled process, in process annealing operation, according to copper material separately, the thickness of copper bar, is kept 30 seconds～2 minutes with the temperature of approximately 600 ℃～800 ℃.In addition, in blank anneal operation, also, according to copper material separately, the thickness of blank material, with the temperature of approximately 500～750 ℃, blank is kept approximately 30 seconds～2 minutes.Like this, even if for example material is identical, because thermotolerance can change according to the difference of the thickness of copper material, therefore can make temperature reduce along with thickness attenuation.

In addition, below total degree of finish of the thickness t of the material corresponding in final cold rolling process and the rolled copper foil that finally obtains is shown in.

● used the rolled copper foil of tough pitch copper: total degree of finish 90.0%～91.8%

·t8.0μm：t80μm→（90.0%）→t8.0μm

·t11.0μm：t125μm→（91.2%）→t11.0μm

·t16.5μm：t200μm→（91.8%）→t16.5μm

·t17.0μm：t200μm→（91.5%）→t17.0μm

● used the rolled copper foil of oxygen free copper: total degree of finish 94.3%～94.6%

·t8.0μm：t140μm→（94.3%）→t8.0μm

·t11.0μm：t200μm→（94.5%）→t11.0μm

·t16.5μm：t300μm→（94.5%）→t16.5μm

·t17.0μm：t315μm→（94.6%）→t17.0μm

● used the rolled copper foil of the tough pitch copper that is added with Ag: total degree of finish 96.9%～97.8%

·t8.0μm：t360μm→（97.8%）→t8.0μm

·t11.0μm：t400μm→（97.3%）→t11.0μm

·t16.5μm：t550μm→（97.0%）→t16.5μm

·t17.0μm：t550μm→（96.9%）→t17.0μm

● used the rolled copper foil of the oxygen free copper that is added with Sn: total degree of finish 96.9%～97.8%

·t8.0μm：t360μm→（97.8%）→t8.0μm

·t11.0μm：t400μm→（97.3%）→t11.0μm

·t16.5μm：t550μm→（97.0%）→t16.5μm

·t17.0μm：t550μm→（96.9%）→t17.0μm

(with the making of the rolled copper foil of copper coating)

Below, the rolled copper foil obtaining is as mentioned above implemented to copper facing, make the rolled copper foil with copper coating.

First, in the electrolytic degreasing that the surface of rolled copper foil is cleaned, in the aqueous solution that contains sodium hydroxide 40g/L, sodium carbonate 20g/L, at 40 ℃ of liquid temperatures, current density 10A/dm ²condition under carry out processing for 10 seconds.

In and the basic solution of the remained on surface of rolled copper foil removing in the cleanup acid treatment of oxide film of copper, in the aqueous solution that contains sulfuric acid 150g/L, under the condition of 25 ℃ of liquid temperatures, flood 10 seconds.

Enforcement is usingd rolled copper foil as the electrolysis treatment of negative electrode, forms respectively copper coating: the copper coating that forms thickness 0.1 μ m for the rolled copper foil of 8.0 μ m; For the rolled copper foil of thickness 11.0 μ m, form the copper coating of thickness 0.4 μ m; For the rolled copper foil of thickness 16.5 μ m, form the copper coating of thickness 0.7 μ m; For the rolled copper foil of thickness 17.0 μ m, form the copper coating of thickness 1.0 μ m.The thickness that increases and decreases copper coating in the thickness of increase and decrease rolled copper foil is the viewpoint for production, production cost, and itself is the effect of left and right the present embodiment not.

Now, in embodiment 1～32 and a part of comparative example, change the addition of the SPS adding in electroplate liquid.In addition,, in a part of comparative example, do not carry out the interpolation of SPS.Following table 2 shows the detailed conditions in copper facing.

[table 2]

Under the condition of table 2, in embodiment and comparative example, all obtain the copper coating of the flatness with equal extent.The surfaceness of copper coating is with 10 mean roughness Rzjis(JIS B0601:2001) count 0.4 μ m～0.7 μ m.

By above operation, obtain rolled copper foil and use the embodiment 1～8 of tough pitch copper and comparative example 1～4, the embodiment 9～16 of rolled copper foil use oxygen free copper and embodiment 17～24 and comparative example 9～12, the rolled copper foil that comparative example 5～8, rolled copper foil are used the tough pitch copper that is added with Ag to use the embodiment 25～32 of the oxygen free copper that is added with Sn and the rolled copper foil with copper coating that comparative example 13～16 relates to.

(2) X-ray diffraction carrying out according to 2 θ/θ method

Copper coating, the rolled copper foil of the rolled copper foil with copper coating relating to for the above-mentioned embodiment obtaining like that and comparative example, utilize X-ray diffraction device to measure crystalline orientation.About the crystalline orientation of rolled copper foil, with the state forming before copper coating, measure.As X-ray diffraction device, use the X-ray diffraction device (model: Ultima IV) of Co., Ltd. Neo-Confucianism's system.Table 3 gathers demonstration condition determination.

[table 3]

When measuring the crystalline orientation of copper coating, according to the thickness of copper coating, suitably change the output rating, slit of X ray etc.Particularly, it is thinner that copper coating becomes, and makes output rating less, and, make slit width and slot angles less.Here, as the present invention relates to 111} face, 002} face, the scope of the mensuration angle of 022} face (2 θ), although 40 °～80 ° be fully, measure and carry out between 40 °～140 °.By like this, obtain as 2 θ and 80 ° be in a ratio of high angle side crystal plane { 113} face, { 133} face, { information of 024} face as a reference.By the mensuration of high angle side, { 113} face, { 133} face, { diffraction peak intensity of 024} face is minimum to confirm this.Thus, confirm these crystal planes on almost not impact of resistance to bend(ing), even if do not consider also passable.

First, the measurement result of the typical example in 4 kinds of different rolled copper foils such as above-mentioned starting material, total degree of finish is shown in to following table 4 and Fig. 2～Fig. 5.So-called 4 kinds of rolled copper foils, that is, used tough pitch copper rolled copper foil, used oxygen free copper rolled copper foil, used the tough pitch copper that is added with Ag rolled copper foil, used the rolled copper foil of the oxygen free copper that is added with Sn.The manufacturing conditions of rolled copper foil is made as common in embodiment and comparative example, and all the measurement result of embodiment and comparative example is all embodied in these 4 kinds of typical examples.

[table 4]

The measurement result of the copper coating in addition, embodiment 1～32 and comparative example 1～16 being possessed is shown in following table 5～table 8 and Fig. 6～Figure 17.That is, table 5 is that rolled copper foil is used the embodiment 1～8 of tough pitch copper and the result of comparative example 1～4.In addition, table 6 is that rolled copper foil is used the embodiment 9～16 of oxygen free copper and the result of comparative example 5～8.In addition, table 7 is that rolled copper foil is used the embodiment 17～24 of tough pitch copper and the result of comparative example 9～12 that is added with Ag.In addition, table 8 is that rolled copper foil is used the embodiment 25～32 of oxygen free copper and the result of comparative example 13～16 that is added with Sn.In each table, as " important document that formula (1)～(6) relate to ", meeting formula (1), and, meet in the situation of at least arbitrary state in formula (2), (3) or (4), (5) or (6), be designated as " meeting ".In addition in the situation that meet at least one in following situation, be designated as, " not meeting ": do not meet the situation of formula (1) or also do not meet the situation of at least arbitrary state in formula (2), (3) or (4), (5) or (6).

[table 5]

[table 6]

[table 7]

[table 8]

According to table 5～table 8, the rolled copper foil of 4 kinds of copper materials in embodiment and its material are irrelevant, also irrelevant with thickness in addition, all meet formula (1).Further meet at least arbitrary state in formula (2), (3) or (4), (5) or (6).

In addition, on the other hand, the rolled copper foil of 4 kinds of copper materials during copper facing in the few or un-added comparative example of the addition of SPS and its material are irrelevant, also irrelevant with thickness in addition, all outside the scope of formula (1).Further, in formula (2)～formula (5) also all outside specialized range.Here, from the measurement result of these comparative examples, the important document (>=15.0) in above-mentioned formula (1) is the value with suitable enough and to spare.Therefore whether can say singly with regard to formula (1), according to copper coating, whether meet formula (1), be that the crystalline structure same with rolled copper foil is with regard to clear enough.

(3) flexible life test

Then, for to each rolled copper foil with respectively study with the resistance to bend(ing) of the rolled copper foil of copper coating, carry out flexible life test, measure each rolled copper foil and respectively with the rolled copper foil of copper coating until the alternating bending frequency (bend fracture number of times) of fracture.This test is used FPC high speed bend test machine (model: SEK-31B2S), according to the IPC(U.S. printed electronic circuit association) standard of Shinetsu Eng Co., Ltd. (エ of SHIN-ETSU HANTOTAI Application ジ ニアリン グ Co., Ltd.) system to carry out.Figure 18 shows the schematic diagram of the general slip bend test device 10 comprise such FPC high speed bend test machine etc.

First, for by respectively with the rolled copper foil of copper coating and do not have each rolled copper foil of copper coating to be cut into width 12.5mm, length 220mm(220mm in rolling direction) coupons 50, copy above-mentioned recrystallization annealing operation, 300 ℃, the enforcement recrystallization annealing of 5 minutes.An example of the actual heat bearing of rolled copper foil when closely sealed with base material in the CCL operation of described condition imitation flexible printing wiring board.

Then, as shown in figure 18, coupons 50 use screws 12 are fixed on to the sample retaining plate 11 of slip bend test device 10.Then, make coupons 50 contact vibration transport parts 13 and paste, utilizing vibration driving body 14 that vibration transmission portion 13 is vibrated on above-below direction, thereby make vibration transmission to coupons 50, implementing flexible life test.As the condition determination of flexible life, bending radius 10r is made as to 1.5mm, stroke 10s is made as to 10mm, frequency is made as to 25Hz.Under this condition, to each coupons 50 each 3 measure, to until there is the mean value of the number of times (bend fracture number of times) of fracture and compare.

By by the measurement result obtaining like this, the measurement result of the monomer of different 4 kinds of rolled copper foils such as above-mentioned starting material, total degree of finish is shown in to following table 9.The numerical value of the bend fracture number of times in table 9 is the mean value of every kind of each measurement result of 3.

[table 9]

4 kinds of rolled copper foils separately total degree of finish of final cold rolling process are more than 90%; As preferred condition, be more than 94%; As further preferred condition, be more than 96%.Therefore known, according to the height of total degree of finish, become separately the rolled copper foil with excellent resistance to bend(ing).

In addition, for respectively, with the rolled copper foil of copper coating, the measurement result obtaining is shown in to following table 10～table 13.That is, table 10 is that rolled copper foil is used the embodiment 1～8 of tough pitch copper and the result of comparative example 1～4.In addition, table 11 is that rolled copper foil is used the embodiment 9～16 of oxygen free copper and the result of comparative example 5～8.In addition, table 12 is that rolled copper foil is used the embodiment 17～24 of tough pitch copper and the result of comparative example 9～12 that is added with Ag.In addition, table 13 is that rolled copper foil is used the embodiment 25～32 of oxygen free copper and the result of comparative example 13～16 that is added with Sn.Here, the numerical value of the bend fracture number of times in each table is the mean value of every kind of each measurement result of 3.In addition, right-hand member of each table show with respect to the bend fracture number of times of rolled copper foil monomer respectively with the rate of descent of the bend fracture number of times of the rolled copper foil of copper coating.

[table 10]

[table 11]

[table 12]

[table 13]

In each table, mix the measured value that has the different rolled copper foil with copper coating of thickness herein.With the thickness of the rolled copper foil of copper coating, to until the bend fracture number of times of fracture, be that resistance to bend(ing) exerts an influence, therefore need to be careful.That is,, if material is substantially identical, so generally speaking, thickness is thicker until the bend fracture number of times of fracture is fewer.Therefore,, in the respectively rolled copper foil with copper coating shown in each table, whole thickness (total thickness), the thicker resistance to bend(ing) of thickness of rolled copper foil monomer are lower.The not so large impact of the thickness of the copper coating that here, bed thickness is thin with respect to rolled copper foil itself.

Rolled copper foil is used in the embodiment 1～32 of 4 kinds of copper materials, with the rolled copper foil of copper coating resistance to bend(ing) as a whole, all than corresponding with it comparative example, significantly improves.In addition, from the improvement degree (level) of the resistance to bend(ing) of the rolled copper foil with copper coating of the rolled copper foil corresponding to 4 kinds of copper materials, do not depend on copper material, the resistance to bend(ing) of rolled copper foil, copper coating is got over Bao Yuehao.

In following table 14, these measurement results of embodiment 1～32 and comparative example 1～16 are gathered to demonstration according to the thickness of copper coating and rolled copper foil.In addition, in Figure 19, the rolled copper foil of 4 kinds of copper materials that relate to for embodiment 1～32 respectively, the relation of present in diagrammatic form thickness and bend fracture number of times.The transverse axis of chart is the thickness (μ m) of rolled copper foil, and the longitudinal axis is bend fracture number of times (inferior).In addition, the △ mark on chart is the example that rolled copper foil is used tough pitch copper.In addition, mark is the example that rolled copper foil is used oxygen free copper.In addition, ◆ mark is the example that rolled copper foil is used the tough pitch copper that is added with Ag.In addition, 〇 mark is the example that rolled copper foil is used the oxygen free copper that is added with Sn.

[table 14]

According to table 14, with respect to the bend fracture number of times of rolled copper foil monomer, with the rate of descent of the bend fracture number of times of the rolled copper foil of copper coating, in arbitrary thickness, be embodiment fewer than comparative example.

In addition, as from Figure 19 clearly, generally speaking, lower from the thicker bend fracture of thickness between copper material number of times.Herein, no matter the crystalline structure of copper coating, characteristic how, exist, only by giving copper coating, thickness increases caused, the impact on bend fracture number of times to the rolled copper foil with copper coating that embodiment and comparative example relate to.That is,, even in the copper coating of expectation, compare with the situation of rolled copper foil monomer, bend fracture number of times also must reduce.

Based on this kind of situation, from the measurement result of embodiment, the rolled copper foil with copper coating that embodiment relates to is all very little with respect to the rate of descent of the bend fracture number of times of rolled copper foil monomer, can think and almost only be subject to the impact of thickness increasing portion.That is, can think and produce hardly the detrimentally affect that crystalline structure by copper coating etc. causes.

On the other hand, the measurement result of or un-added comparative example few from the addition of SPS, rate of descent with respect to the bend fracture number of times of rolled copper foil monomer is all very large, the detrimentally affect that shown to produce impact beyond the impact of thickness increasing portion, is caused by the crystalline structure of copper coating etc.

Known as mentioned above, by the rolled copper foil for after final cold rolling process, before recrystallization annealing operation, form and the copper coating of taking the different orientation of epitaxially grown crystalline orientation to have occurred, do not taked to organize with rolling set equal crystalline orientation, can improve the resistance to bend(ing) with the rolled copper foil of copper coating.

In addition, think in the addition of when obtaining such copper coating SPS used, have preferred scope.At least, in the scope of the present embodiment, when the SPS of every 1 liter of electroplate liquid addition is 20mg～150mg, can confirm sufficient effect, within the scope of this, not find the difference of effect.In addition, at SPS, be 10mg when following, completely unconfirmed to effect of the present invention.Therefore, can think and surpassing 10mg and be less than in the scope of 20mg, have the main points of performance effect of the present invention.In addition,, even if infer in the situation that SPS surpasses 150mg, also can continue within the specific limits to obtain effect of the present invention., the viewpoint of the cost producing from production, additive, for the SPS adding more than 150mg, unconfirmed to advantage.

In sum, the lower value as the SPS amount of every 1 liter of electroplate liquid, can be made as the 20mg that effect is clear and definite.In addition, the higher limit as the SPS amount of every 1 liter of electroplate liquid, can be made as 150mg.

Here, as mentioned above, the combination of rolled copper foil and copper coating formed thereon can not be also the combination shown in the present embodiment.For example, the copper coating of thickness 1.0 μ m can be on the rolled copper foil of thickness 8.0 μ m, given, also the copper coating of thickness 0.1 μ m can be on the rolled copper foil of thickness 17.0 μ m, given.In such formation, also can obtain effect of the present invention as described above.

Claims (5)

1. with a rolled copper foil for copper coating, it is characterized in that,

It possesses: major surfaces or the back side have after the final cold rolling process of parallel a plurality of crystal planes, the rolled copper foil before recrystallization annealing operation, with be formed on the major surfaces of described rolled copper foil or the face of at least one side in its back side, major surfaces or become the copper coating with the back side at the interface of described rolled copper foil with parallel a plurality of crystal planes

In described a plurality of crystal planes of described rolled copper foil, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _r{ 111}, I _r{ 002}, I _r022}, by the mark P of the intensity level of diffraction peak described in each _r{ 111}, P _r{ 002}, P _r022} is made as:

P _R{111}=[I _R{111}/(I _R{111}+I _R{002}+I _R{022})]×100、

P _R{002}=[I _R{002}/(I _R{111}+I _R{002}+I _R{022})]×100、

P _R{022}=[I _R{022}/(I _R{111}+I _R{002}+I _R{022})]×100，

In described a plurality of crystal planes of described copper coating, by by { 111} face, { 002} face, { intensity level of the diffraction peak that X-ray diffraction that 022} face carries out according to 2 θ/θ method obtains is made as I separately _m{ 111}, I _m{ 002}, I _m022}, by the mark P of the intensity level of diffraction peak described in each _m{ 111}, P _m{ 002}, P _m022} is made as:

P _M{111}=[I _M{111}/(I _M{111}+I _M{002}+I _M{022})]×100、

P _M{002}=[I _M{002}/(I _M{111}+I _M{002}+I _M{022})]×100、

P _M{022}=[I _M{022}/(I _M{111}+I _M{002}+I _M{022})]×100

Time,

Become at least arbitrary state in following state:

Meet following formula (1)

P _M{111}≥15.0…（1），

Further meet following formula (2)

P _m{ 111}>(P _r111}+5) ... (2) state;

Meet following formula (3), (4)

P _M{002}<（P _R{002}-10）…（3）

P _M{002}>（P _R{002}+10）…（4）

In any state;

Meet following formula (5), (6)

P _M{022}<（P _R{022}-10）…（5）

P _M{022}>（P _R{022}+10）…（6）

In any state.

2. the rolled copper foil with copper coating according to claim 1, is characterized in that, meet in following formula (2), (4), (6) at least any:

P _M{111}>（P _R{111}+5）…（2）

P _M{002}>（P _R{002}+10）…（4）

P _M{022}>（P _R{022}+10）…（6）。

3. the rolled copper foil with copper coating according to claim 1 and 2, is characterized in that,

Described rolled copper foil is formed by following substances: the fine copper being formed by tough pitch copper or oxygen free copper or the lower concentration copper alloy that tough pitch copper or oxygen free copper is parent phase of take,

Described rolled copper foil is taked the form of fine copper type set tissue.

4. according to the rolled copper foil with copper coating described in any one in claim 1～3, it is characterized in that, the whole thickness of described copper coating and described rolled copper foil is below the above 20 μ m of 1 μ m, and the thickness of described copper coating is below the above 1.0 μ m of 0.1 μ m.

5. according to the rolled copper foil with copper coating described in any one in claim 1～4, it is characterized in that, it is the rolled copper foil with copper coating for flexible printing wiring board.