CN103826765B

CN103826765B - Rolling copper foil

Info

Publication number: CN103826765B
Application number: CN201280047253.3A
Authority: CN
Inventors: 中室嘉一郎; 千叶喜宽; 大久保光浩; 鲛岛大辅; 冠和树; 青岛一贵
Original assignee: JX Nippon Mining and Metals Corp
Priority date: 2011-09-27
Filing date: 2012-08-28
Publication date: 2016-05-11
Anticipated expiration: 2032-08-28
Also published as: KR20140061453A; CN103826765A; KR101586594B1; JP2013071139A; JP5758254B2; WO2013047053A1; TW201315549A; TWI462787B

Abstract

A kind of rolling Copper Foil is provided, and it makes copper foil surface, and moderately roughening is to improve treatability, and bendability is outstanding, and surface etching characteristic is good. For a kind of rolling Copper Foil, wherein, the 60 surperficial degree glossiness (G60 that measure along rolling parallel direction_RD) be more than 100 and below 300, taking 200 DEG C of heating 30 minutes and modified under the state of recrystallized structure, 200 diffracted intensities (I) of trying to achieve by X-ray diffraction of plane roll are with respect to the 200 diffracted intensity (I that try to achieve by X-ray diffraction of micropowder copper₀) be 20≤I/I₀≤ 40, be that copper foil surface place is 175 μ m along rolling parallel direction length, and along on 3 more than rolling right angle orientation difference interval 50 μ m straight lines, the maximum height of thickness direction of each straight line and the mean value (d) of the difference of minimum constructive height suitable with the depth capacity in oil hole are below 0.1 with the ratio (d/t) of the thickness (t) of described Copper Foil, the 60 surperficial degree glossiness (G60 that measure along rolling parallel direction_RD) with the surperficial 60 degree glossiness (G60 that measure along rolling right angle orientation_TD) ratio (G60_RD/G60_TD) be less than 0.8.

Description

Rolling Copper Foil

Technical field

The present invention relates to be suitable for the rolling Copper Foil of the FPC that requires bendability.

Background technology

Bending requires high bendability with the Copper Foil that FPC (flexible printed circuit board) uses. As the method for Copper Foil being given to bendability, known to Copper Foil plane roll improve the degree of orientation of the crystal orientation of (200) face technology (patent documentation 1), improve the technology (patent documentation 2) of the ratio of the crystal grain connecting along the thickness of slab direction of Copper Foil, the surface roughness Ry (maximum height) suitable with the degree of depth in the oil hole (oilpit) of Copper Foil be reduced to the technology (patent documentation 3) below 2.0 μ m.

General FPC manufacturing process is as follows. First Copper Foil is engaged with resin molding. In joint, have by be coated on glue (varnish) on Copper Foil implement heat treatment carry out the method for imidization (イミ De), by the resin molding with bonding agent and the overlapping and stacked method of Copper Foil. The Copper Foil of the tape tree adipose membrane engaging by these operations is called to CCL (copper-clad laminated board). By the heat treatment in this CCL manufacturing process, Copper Foil recrystallization.

In addition, in the time using Copper Foil to manufacture FPC, if the close property of raising and covering layer film (coverlayfilm) and etching copper foil surface, sometimes there is the depression (dish falls into (dishdown)) of diameter number 10 μ m left and right on surface, and especially easily betide high bending Copper Foil. Its reason is because in order to give high bendability, organize the crystal orientation of flourishing mode control Copper Foil with the cube after recrystallization annealing. That is, can think, this is because even if carry out this kind of control, the orientation of crystallization can be all not consistent yet, has partly the different crystal grain of crystal orientation uniformly in tissue. Now, etching speed because of etched crystal plane different, thereby this crystal grain compared with around by part etching deeper, become depression. This depression becomes the etching that reduces circuit, or in visual examination, is judged as reason bad and reduction yield rate.

In addition, according to etching solution, cube tissue is compared with random organization, and etching speed exists situation about accelerating and slack-off situation. Thereby too flourishing if the cube after recrystallization annealing is organized, the etching speed of this cube tissue is slack-off, thus productivity ratio reduce, or when circuit formation between circuit remaining copper, etching is deteriorated. On the other hand, if the etching speed of cube tissue accelerates, be easily etched to circuit part, etching still can be deteriorated.

As the method that alleviates this kind of depression, report has before rolling or after rolling carries out mechanical lapping to apply the technology (patent documentation 4) that becomes recrystallization after the strain of affected layer to the surface of Copper Foil. According to this technology, utilize affected layer after recrystallization, to make inhomogeneous crystal grain mass-send in surface, make not individualism of the different crystal grain of crystal orientation.

Prior art document

Patent documentation

Patent documentation 1: No. 3009383 communique of Japanese Patent;

Patent documentation 2: TOHKEMY 2006-117977 communique;

Patent documentation 3: TOHKEMY 2001-058203 communique;

Patent documentation 4: TOHKEMY 2009-280855 communique.

Summary of the invention

The problem to be solved in the present invention

But the technology of recording at patent documentation 4, there are the following problems, that is, inhomogeneous crystal grain is more, and the crystallization of copper foil surface is not along (100) planar orientation, thereby bendability reduces.

On the other hand, during in order to ensure the manufacture of Copper Foil and the close property of roller, or make the processing of Copper Foil goods easy, make the roller roughness in final cold rolling become large so that copper foil surface is coarse, but understand, if make copper foil surface coarse, the degree of orientation of the crystallization of copper foil surface reduces event bendability variation, or it is sunken easily to produce dish.

That is, the present invention is for having addressed the above problem, and its object is to provide a kind of rolling Copper Foil, and it makes copper foil surface, and moderately roughening is to improve treatability, and bendability is outstanding, and surface etching characteristic is good.

The scheme of dealing with problems

The present invention has carried out various research, found that: the final mill train (pass) at final cold rolling does not nearby make the surface of Copper Foil too coarse, in the final mill train of final cold rolling, make the rough surface of Copper Foil, thereby make final copper foil surface coarse, and reduce detrusion band, maintain bendability, and dish falls into and tails off, poor the diminishing of etching speed based on etching solution, thereby become the outstanding Copper Foil of etching.

To achieve these goals, in rolling Copper Foil of the present invention, the surperficial 60 degree glossiness G60 according to JIS-Z8741 that measure along rolling parallel direction_RDBe more than 100 and below 300, taking 200 DEG C of heating 30 minutes and modified under the state of recrystallized structure, 200 diffracted intensities (I) of trying to achieve by X-ray diffraction of plane roll are with respect to the 200 diffracted intensity (I that try to achieve by X-ray diffraction of micropowder copper₀) be 20≤I/I₀≤ 40, be that copper foil surface place is 175 μ m along rolling parallel direction length, and along on 3 more than rolling right angle orientation difference interval 50 μ m straight lines, the ratio d/t of the maximum height of thickness direction of each straight line suitable with the depth capacity in oil hole and the thickness t of the mean value d of the difference of minimum constructive height and described Copper Foil is below 0.1, the 60 surperficial degree glossiness G60 that measure along rolling parallel direction_RDWith the surperficial 60 degree glossiness G60 according to JIS-Z8741 that measure along rolling right angle orientation_TDRatio G60_RD/G60_TDBe less than 0.8.

It is desirable to, in the case of utilizing EBSD to observe above-mentioned 200 DEG C × 30 minutes copper foil surfaces after heat treatment after electrolytic polishing, the crystal orientation of plane roll is 30～70% with the area occupation ratio that the differential seat angle in [100] orientation is crystal grain more than 15 degree

It is desirable to, after by hot ingot bar rolling, repeat cold rolling and annealing, finally carry out final cold rolling and manufacture, in this final cold rolling operation, the 60 surperficial degree glossiness G60 that measure along rolling parallel direction in the stage before 1 mill train of final mill train_RDExceed 300.

The effect of invention

According to the present invention, can obtain a kind of rolling Copper Foil, it makes copper foil surface, and moderately roughening is to improve treatability, and bendability is outstanding, and surface etching characteristic is good.

Brief description of the drawings

Fig. 1 is the figure that the relation of oil hole and glossiness is shown.

Fig. 2 is the figure that the assay method of the mean value d suitable with the depth capacity in oil hole is shown.

Fig. 3 illustrates the figure that utilizes bend test device to carry out the method for measuring of flexible life.

Detailed description of the invention

Below, the rolling Copper Foil that embodiments of the present invention are related is described. In addition, in the present invention, only otherwise special declaration, % represents quality %.

First, technological thought of the present invention is described. If make the roller roughness in final cold rolling become large so that copper foil surface is coarse, the treatability of Copper Foil improves, and falls into but become easy generation dish, and etching reduces. Can think, this be because, utilize the coarse roller in final cold rolling, on the thickness direction of Copper Foil, produce detrusion band, rolling further continues thereby the prosperity of detrusion band.

On the other hand, the known gimmick that improves glossiness (surface roughness) in order to obtain the bendability of Copper Foil all the time. Can think, this is because be difficult to produce detrusion band by utilizing the roller that roughness is low to carry out final cold rolling, becoming on the thickness direction of Copper Foil. But if improve the glossiness (reduction surface roughness) of Copper Foil, the treatability of Copper Foil reduces.

On the other hand, the inventor has found, final mill train at final cold rolling does not nearby make the surface of Copper Foil too coarse (for example, utilize the roller that roughness is low to carry out rolling), in the final mill train of final cold rolling, make the rough surface (for example, utilizing coarse roller to carry out rolling) of Copper Foil, thereby make final copper foil surface coarse, and reduce detrusion band, improve bendability, and surface etching characteristic becomes good.

Known, in the past, thought that the orientation of Copper Foil only depends on the roughness of copper foil surface always, but in fact the scale of the detrusion band of material internal affects etching and the degree of orientation (and dish falls into). And, in final cold rolling, if suppress fully the prosperity of shear band in can the mill train before final mill train, even if fine finishining copper foil surface cursorily in final mill train also can obtain the degree of orientation that makes etching good.

In addition, only with the value of the glossiness using all the time, can not grasp clearly the flourishing degree of above-mentioned shear band. ; if although think that to make final copper foil surface coarse; and reduce detrusion band; oil hole is shallow and have a width of certain degree; and the Frequency in oil hole tails off (with reference to Fig. 1 (a)), but this is difficult to find expression in the glossiness of the rolling parallel direction RD vertical with the direction in oil hole. On the other hand, if from rolling right angle orientation TD, because oil hole has the width of certain degree, therefore be easy to grasp the shape in oil hole, the variation of frequency from parallel direction.

The relation of this kind of oil hole and glossiness is described with reference to Fig. 1.

First, Fig. 1 (a) represents the oil hole of the inventive example and the figure of the relation of glossiness, if measure glossiness G along rolling parallel direction RD_RD, locate catoptrical direction in oil hole and change and be not detected glossiness step-down. On the other hand, measuring glossiness G along rolling right angle orientation TD_TDSituation under, because extend along TD in oil hole, therefore to side, (RD direction) skew is also detected although locate catoptrical direction in oil hole, glossiness uprises. , with G_RDCompare G_TDRelatively uprise, spend glossiness if measure aftermentioned 60, meet G60_RD/G60_TDThe relation of < 0.8.

Then, Fig. 1 (b) represents the oil hole of the conventional example in the coarse situation of copper foil surface and the figure of the relation of glossiness, the degree of depth and length (Frequency) that copper foil surface becomes excessively coarse and oily hole increase, no matter along any one the mensuration glossiness in rolling parallel direction RD and rolling right angle orientation TD, catoptrically at oil hole place all change thereby be not detected glossiness step-down. In this case, with G_RDCompare G_TDStep-down relatively, spends glossiness if measure aftermentioned 60, meets G60_RD/G60_TDThe relation of > 1.

On the other hand, Fig. 1 (c) represents the oil hole of the conventional example in situation that copper foil surface is level and smooth and the figure of the relation of glossiness, becomes shallow, therefore even measure glossiness G along rolling parallel direction RD because copper foil surface becomes too level and smooth thereby oil hole_RD, locate in oil hole catoptrical direction also become be difficult to change, glossiness uprises. , with G_TDCompare G_RDRelatively uprise, spend glossiness, G60 if measure aftermentioned 60_RD/G60_TDRelation approach 1 (, the anisotropy of RD and TD diminishes). But copper foil surface is coarse unlike Fig. 1 (b) of the coarse conventional example of copper foil surface, thereby is G60_RD/G60_TD＜1。

Regulation and the composition of rolling Copper Foil of the present invention then, are described.

(1) glossiness G60_RD

Make the 60 ° of surperficial glossiness G60 that measure along rolling parallel direction RD_RDBe more than 100 and below 300. If G60_RDExceed 300, copper foil surface becomes too level and smooth, close property reduction when Copper Foil is manufactured and roller, or be difficult to process Copper Foil goods. On the other hand, if G60_RDBe less than 100, copper foil surface becomes too coarse, at material internal, the prosperity of detrusion band, thus become easy generation dish fall into, etching reduce.

(2)G60_RD/G60_TD

As mentioned above, nearby do not make the surface of Copper Foil too coarse at the final mill train of final cold rolling, in the final mill train of final cold rolling, make the rough surface of Copper Foil, thereby make final copper foil surface coarse, and reduce detrusion band, maintain bendability, and dish falls into and tails off. And, understand by the inventor's experiment (aftermentioned embodiment), in the less surface of this kind of detrusion band, G60_RD/G60_TD< 0.8. Thereby, by the 60 ° of surperficial glossiness G60 that measure along rolling parallel direction_RDWith the 60 ° of surperficial glossiness G60 that measure along rolling right angle orientation_TDRatio G60_RD/G60_TDBe defined as and be less than 0.8. In addition adopt than being impact in order to offset overall glossiness.

If G60_RD/G60_TD>=0.8, as above-mentioned Fig. 1 (b), it is too level and smooth that copper foil surface becomes, and when the manufacture of Copper Foil reduces with close property roller, or be difficult to process Copper Foil goods. In addition, if become G60 as above-mentioned Fig. 1 (c)_RD/G60_TD> 1, copper foil surface becomes too coarse, and the prosperity of detrusion band thereby bendability reduce, or become and be easy to produce dish and fall into.

In addition, as making G60_RD/G60_TDThe method of < 0.8, as described above, in final cold rolling, in mill train before final mill train, suppress the prosperity of shear band, in the mill train before the final mill train of final cold rolling, use the smaller roller of roughness (surface roughness Ra is for for example below 0.5 μ m) to carry out rolling. On the other hand, on the other hand, in the final mill train of final cold rolling, use the larger roller of roughness (surface roughness Ra is for for example more than 0.6 μ m) to carry out rolling, make the final copper foil surface obtaining coarse.

At this, in final cold rolling, if make the surperficial glossiness G60 measuring along rolling parallel direction in the stage before 1 mill train of final mill train_RDExceed 300,, in the mill train before the final mill train of final cold rolling, it is smoother that copper foil surface becomes, and is difficult to import detrusion band, because of but desirable.

(3)d/t

If the thickness t attenuation of Copper Foil, even identical surface roughness, the ratio that concave-convex surface occupies copper thickness also becomes greatly, thereby can not fully carry out based on above-mentioned G60_RD/G60_TDThe evaluation of copper foil surface. Therefore in the present invention,, by being defined as d/t≤0.1, can not carry out the evaluation of copper foil surface according to the thickness of Copper Foil.

At this, d is at three straight line L₁～L₃The suitable each straight line L of depth capacity upper and oil hole₁～L₃The maximum height H of thickness direction_MWith minimum constructive height H_SThe mean value of difference di, straight line L₁～L₃Be 175 μ m at copper foil surface place along rolling parallel direction RD length as illustrated in fig. 2, and along more than rolling right angle orientation TD difference interval 50 μ m. Particularly, according to contact roughness, measure L₁～L₃On thickness direction profile and ask maximum height H_MWith minimum constructive height H_S, by each straight line L₁～L₃Di on average.

The thickness of Copper Foil (or copper alloy foil) is restriction especially not, but can use aptly for example Copper Foil of 5～50 μ m.

(4)I/I₀

In order to give high bendability to Copper Foil of the present invention, taking 200 DEG C of heating 30 minutes and modified under the state of recrystallized structure, the 200 diffracted intensity (I that try to achieve by X-ray diffraction by 200 diffracted intensities (I) of trying to achieve by X-ray diffraction of plane roll with respect to micropowder copper₀) be defined as 20≤I/I₀≤ 40. Thus, the degree of orientation of (200) face becomes appropriate value, obtains the outstanding Copper Foil of balance of bendability and etching. In this case, because the recrystallization set of the crystal orientation with (200) face is organized too inflourishing, therefore (200) organizing in a way of the orientation beyond face disperseed, because this tissue is fallen into and also diminishes by the dish that etching causes partly. In addition, in order to give higher bendability to Copper Foil of the present invention, it is desirable to, taking 200 DEG C of heating 30 minutes modified under the state of recrystallized structure, make 25≤I/I₀≤40。

If become I/I₀< 20, the degree of orientation of (200) face tails off, and bendability reduces. If become 40 < I/I₀The tissue with the crystal orientation of (200) face increases, it is good that bendability becomes, but (200) the recrystallization set of face is organized too flourishing, thereby the tissue part in orientation beyond (200) face concentrate generation, it is sunken that this tissue becomes large and easy etched and dish occurs, and etching is poor. In addition, in the orientation beyond (200) face and its, etching speed differs widely and also can make etching reduce.

At above-mentioned 200 DEG C, the annealing of 30 minutes is to imitate the temperature history of in CCL manufacturing process, Copper Foil being paid.

In addition,, if one or more that Copper Foil are contained select from the group of Ag, Sn, In, Au, Pd and Mg add up to 30～300wtppm, manageable is 20≤I/I₀≤ 40, because of but desirable.

Be 20≤I/I as management₀≤ 40 method, can for example repeat cold rolling and annealing, utilizing final annealing to make average crystallite particle diameter is 10～20 μ m, afterwards in the time that rolling is product thickness of slab, making total degree of finish is 90～96%, suppresses the prosperity of shear band in the mill train before the final mill train of final cold rolling. In this case, in the mill train before the final mill train of final cold rolling, can use the roller of roughness smaller (surface roughness Ra is for for example below 0.05 μ m) to carry out rolling.

(5) gun parallax based on EBSD

As mentioned above, it is a kind of depression that dish falls into, this depression is the heat treatment in the time passing through Copper Foil to engage with resin molding, the ratio of the different crystal grain individualism in the uniform formation of recrystallization of crystal orientation is many, when etching, this independent crystal grain is formed by etching deeper compared with around. Therefore, as above-mentioned heat treatment, imitate the lower heating Copper Foil of the heat-treat condition of the temperature history in CCL manufacturing process, Copper Foil given (at 200 DEG C 30 minutes) and modified be recrystallized structure. And, as the crystal orientation of this state, it is desirable to, the in the situation that of utilizing EBSD to observe copper foil surface after electrolytic polishing, the crystal orientation of plane roll is 30～70% with the area occupation ratio that the differential seat angle in [100] orientation is crystal grain more than 15 degree.

If above-mentioned area occupation ratio is 30～70% in the situation that utilizing EBSD to observe, can obtain all outstanding Copper Foils of bendability and etching. If it is poor that above-mentioned area occupation ratio is less than 30% etching, if exceed 70% bendability reduction sometimes. In addition, be 30～70% in order to make above-mentioned area occupation ratio in the situation that utilizing EBSD to observe, it is desirable to, as described above, in final cold rolling, in mill train before final mill train, suppress the prosperity of shear band, in the mill train before the final mill train of final cold rolling, use the smaller roller of roughness (surface roughness Ra is for for example below 0.05 μ m) to carry out rolling. In addition, if one or more that Copper Foil are contained select from the group of Ag, Sn, In, Au, Pd and Mg add up to 30～300wtppm, be easily 30～70% by above-mentioned area occupation ratio management, because of but desirable.

In addition, to accepting thermal history and becoming the Copper Foil of CCL, also can at 200 DEG C, heat 30 minutes. Even if the recrystallization that is organized in of heat treated Copper Foil once further heated also and changes hardly before, thereby in the observation that utilizes EBSD, does not distinguish the Copper Foil of accepting the Copper Foil of thermal history and not accepting, with 200 DEG C of heating 30 minutes.

(6) composition

As Copper Foil, can use more than purity 99.9wt% tough pitch copper (タ Off ピッチ Copper), oxygen-free copper, cathode copper, and it is desirable to contain one or more totals 30～300wtppm selecting from the group of Ag, Sn, In, Au, Pd and Mg. Oxygen-free copper is by JIS-H3510 (alloy numbering C1011) and JIS-H3100 (alloy numbering C1020) regulation, and tough pitch copper is by JIS-H3100 (alloy numbering C1100) regulation.

One example of the manufacture method of rolling Copper Foil of the present invention then, is described. First, after by the hot rolling of ingot bar of the alloying element that comprises copper and necessity and inevitable impurity, repeat cold rolling and annealing, finally utilizing final cold rolling fine finishining is set thickness.

At this, as mentioned above, nearby do not make the surface of Copper Foil too coarse at the final mill train of final cold rolling, in the final mill train of final cold rolling, make the rough surface of Copper Foil, thereby make final copper foil surface coarse, and reduce detrusion band, improve bendability, and dish fall into tail off. And, in the less surface of this kind of detrusion band, G60_RD/G60_TD＜0.8。

Thereby, at the final mill train of final cold rolling nearby, in order to make copper foil surface too not coarse, smaller roller carries out rolling, or 1 the mill train degree of finish strengthening in final cold rolling carries out rolling to use roughness (surface roughness Ra is for example that 0.5 μ m is following). On the other hand, in the final mill train of final cold rolling, use the larger roller of roughness (surface roughness Ra is for for example more than 0.6 μ m) to carry out rolling, or use the high rolling oil of viscosity to carry out rolling, make the final copper foil surface obtaining coarse.

In addition, in order to make final copper foil surface coarse, and reduce detrusion band, need in final 2 mill traines of final cold rolling or final mill train, use as described above coarse roller or use the high rolling oil of viscosity to carry out rolling, but it is desirable to adjust the rolling condition in final mill train, adjust because be easy to. On the other hand, if started in the past to make the roughness chap of roller, detrusion band prosperity from final 3 mill traines of final cold rolling.

In addition, under capable of regulating annealing conditions so that the average grain diameter of the recrystallization grain that the annealing before utilizing final cold rolling tight obtains becomes 10～20 μ m. In addition, can make the rotary rolling mill degree in final cold rolling is 92～99%.

Embodiment

The element that cathode copper interpolation table 1 is recorded has been cast blank (ingot) in (mist of N2 and CO) (embodiment 4,6,7～14) in (embodiment 1～3,5) and reducing atmosphere respectively in atmosphere. In addition, comparative example 1～5 has been cast blank in argon gas atmosphere. The oxygen that the blank of casting in atmosphere contains 150～300ppm, the blank of casting in reduction atmosphere contains the oxygen with oxygen-free copper (C1020) same degree. The blank of made is carried out to hot rolling until thickness 10mm above at 800 DEG C, after surperficial oxidation surface is eliminated, repeat cold rolling and annealing, after the thickness that becomes 0.24mm (embodiment 1～12), 0.12mm (embodiment 13), 0.36mm (embodiment 14), 1.2mm (comparative example 1～5), anneal so that average crystallite particle diameter is 13 μ m respectively afterwards. And utilize final cold rolling fine finishining for thickness 0.012m (embodiment 1～12, comparative example 1～5), 0.006mm (embodiment 13), 0.018mm (embodiment 14). In addition, making the degree of finish of the final cold rolling of embodiment 1～14 is 95%, and the degree of finish that makes the final cold rolling of comparative example 1～5 is 99%.

In addition, final cold rolling carries out 5～15 mill traines, as shown in table 1, changes the surface roughness of roller of final mill train before nearby and the surface roughness of the roller of final mill train and carries out rolling. From the 1st mill train of final mill train till the surface roughness of the roller nearby of final mill train is all identical.

Each Copper Foil test portion to acquisition like this has carried out the evaluation of each characteristic.

(1) glossiness

Measured respectively the glossiness G60 of copper foil surface according to JIS-Z8741 along rolling parallel direction RD and rolling right angle orientation TD_RD、G60_TD。

(2) cube set tissue

After test portion is heated 30 minutes at 200 DEG C, ask the integrated value (I) of 200 diffracted intensities of trying to achieve by X-ray diffraction of plane roll. Integrated value (I0) by this value divided by 200 diffracted intensities of trying to achieve by X-ray diffraction of the micropowder copper of measuring in advance (325mesh uses after 1 hour with 300 DEG C of heating in hydrogen stream), has calculated I/I0 value.

(3) (mean value d) for the depth capacity in oil hole

Use contact roughmeter (little slope institute system SE-3400), as shown in Figure 2, ask respectively three straight line L₁～L₃On maximum height H_MWith minimum constructive height H_SDifference di, straight line L₁～L₃Be 175 μ m at copper foil surface place along rolling parallel direction length, and along more than rolling right angle orientation TD difference interval 50 μ m. By each straight line L₁～L₃Di on average using as d. In addition, adopt d (mm)/t (mm).

(4) gun parallax based on EBSD

After electrolytic polishing, utilize EBSD (backscattering electric wire diffraction instrument, the JXA8500F of Jeol Ltd., accelerating potential 20kV, electric current 2e-8A, measurement range 1000 μ m × 1000 μ m, walk wide 5 μ and m) have observed in (2) and heated 30 minutes test portion surfaces afterwards with 200 DEG C. Asking with the differential seat angle in [100] orientation by image analysis is the area occupation ratio of crystal grains more than 15 degree. And, by the visual number that exceedes 20 μ m at the range of observation intercrystalline particle diameter of test portion surface 1mm pros of having calculated.

(5) etching

Evaluate as follows etching. First, use etching solution (being respectively ADEKATEC (アデカテッ Network) CL-8 (Asahi Denka Co., Ltd. (アデカ) system) liquid and DP-200 (weak Yuan ユージライト system) liquid) to carry out at normal temperatures etching 2 minutes, by the image light and shade binaryzation of the surface photography of the range of observation of the 1mm pros after utilizing light microscope to etching, calculate the ratio of light and shade. The tissue with [100] orientation is owing to being the face parallel with copper foil surface, thus brighter, under other orientation, tiny concavo-convex owing to producing on surface, therefore that diffuse reflection causes seeming is darker.

Then, state clearly among portion and dark portion upper, ratio is less than to the tissue that a side of 50% regards the side that area occupation ratio is few as. Because the few side's of area occupation ratio tissue is surrounded and exists by the many sides' of area occupation ratio tissue, therefore utilize the side's that polygonal approximation area occupation ratio is few tissue, the minimum diameter that has calculated this polygonal circumscribed circle exceedes the number at the position of 50 μ m. No matter use any liquid of ADEKATECCL-8, DP-200, in range of observation, this position is all below 10, and the test portion by the difference of the etch quantity after 30 minutes after the etch quantity before 30 minutes and final cold rolling after final cold rolling and with 200 DEG C of heating and with 200 DEG C of heating in ± 10% is decided to be etching good (zero), by above-mentioned number, more than 10, or exceed ± 10% test portion of the difference of above-mentioned etch quantity is decided to be etching poor (×).

At this, utilize (the Copper Foil weight after the Copper Foil weight-etching before etching) to calculate etch quantity, if, in ± 10%, thinking, the difference of above-mentioned etch quantity has or not recrystallization after final cold rolling, and etch quantity is all difficult to change, and etching is outstanding.

In addition,, at copper foil surface, compared with bright and dark face mix, any one the many situation in bright or dark face has the good tendency of etching.

(6) scar on surface

, there is 5 places/m by the scar in rolling direction with length more than 10mm in the surface of visual each test portion²Above situation is decided to be ×.

(7) bendability

After test portion being heated 30 minutes with 200 DEG C and makes its recrystallization, to polyimide film (trade name: Kapton(カプト Application) (registration mark) EN) one side (face bonding with Copper Foil) coating 2 μ m thermoplasticity PI bonding agents after dry, formed the thick resin bed of 27 μ m. Copper Foil is laminated in to the binding agent face of this resin bed and carries out Vacuum Heat punching press, made copper-clad laminated body. Utilize the bend test device shown in Fig. 3 to carry out the mensuration of the flexible life of copper-clad laminated body. This device is the structure that vibration transmission member 3 is incorporated into vibration driving body 4, by test Copper Foil 1 the top ends of the part of the screw 2 with shown in arrow and 3 altogether 4 locate to be fixed on device. If vibration section 3 drives up and down, the pars intermedia of Copper Foil 1 is bent into hairpin shape with set radius of curvature r. In this test, the number of times before the fracture while asking under following condition repeated flex.

In addition, experimental condition is as follows: test film width: 12.7mm, test film length: 200mm, test film extracts direction: extract in the mode that the length direction of test film is parallel with rolling direction, radius of curvature r:2.5mm, vibratility adjustment: 25mm, vibration velocity: 1500 beats/min. In addition, be more than 500,000 times in the situation that in flexible life, be judged as and there is outstanding bendability. If flexible life is more than 500,000 times, there is the good bendability of the harsh bending that can tolerate folding movable part of fold type portable telephone etc.

By the table 1 that the results are shown in obtaining.

[table 1]

As shown in Table 1, at G60_RDBe more than 100 and 300 following and 20≤I/I₀≤ 40, and d/t is below 0.1, G60_RD/G60_TDBe less than in 0.8 the situation of each example, etching is outstanding, and copper foil surface do not have scar, and bendability is also good.

On the other hand, be in final cold rolling, make final mill train nearby before the surface roughness of roller and the surface roughness of the roller of final mill train be in the situation of the comparative example 1 below Ra=0.05 μ m, the G60 of copper foil surface_RDExceed 300, produce scar at copper foil surface, treatability is poor.

Be in final cold rolling, make final mill train nearby before the surface roughness of roller coarse to more than Ra=0.06 μ m, the surface roughness that makes the roller of final mill train is in the situation of the comparative example 2 below Ra=0.05 μ m, is I/I₀> 40, the sunken number of dish increases therefore etching reduces, in addition, the G60 of copper foil surface_RDExceed 300, produce scar at copper foil surface, treatability is poor.

Be in final cold rolling, make final mill train nearby before the surface roughness of roller and the surface roughness of the roller of final mill train all coarse in the situation of comparative example 3,4,5 more than Ra=0.6 μ m, be I/I₀> 40, the sunken number of dish increases therefore etching reduces.

In addition, the in the situation that of comparative example 3,4, owing to making, the roll surface roughness of whole mill traines of final cold rolling is coarse, thus at material internal, the prosperity of detrusion band, the degree of orientation of the crystallization of copper foil surface reduces, and becomes I/I₀＞40。

On the other hand, the in the situation that of comparative example 5, due to make final mill train nearby before the roughness ratio comparative example 3,4 of roller level and smooth, therefore glossiness becomes the value higher than comparative example 3,4, but the inhibition of shear band is still insufficient, is I/I₀> 40, the sunken number of dish increases therefore etching reduces. In addition, in the case of make final mill train nearby before roller roughness be to suppress shear band 0.07 μ m, have the plate speed etc. of reduction method, but think that glossiness exceedes 300 in this case, injurious surface mark is judged to be ×.

Claims

1. a rolling Copper Foil, wherein, the surperficial 60 degree glossiness G60 according to JIS-Z8741 that measure along rolling parallel direction_RDBe more than 100 and below 300, taking 200 DEG C of heating 30 minutes and modified under the state of recrystallized structure, the 200 diffracted intensity I that try to achieve by X-ray diffraction of plane roll with respect to 325mesh, in hydrogen stream with 300 DEG C of heating the 200 diffracted intensity I that try to achieve by X-ray diffraction of the micropowder copper after 1 hour₀Be 20≤I/I₀≤40，

On 3 straight lines, the ratio d/t of the maximum height of thickness direction of each straight line suitable with the depth capacity in oil hole and the thickness t of the mean value d of the difference of minimum constructive height and described Copper Foil is below 0.1, described 3 straight lines are 175 μ m at copper foil surface place along rolling parallel direction length, and more than rolling right angle orientation difference interval 50 μ m

The 60 surperficial degree glossiness G60 that measure along rolling parallel direction_RDWith the surperficial 60 degree glossiness G60 according to JIS-Z8741 that measure along rolling right angle orientation_TDRatio G60_RD/G60_TDBe less than 0.8.

2. rolling Copper Foil according to claim 1, wherein, in the case of utilizing EBSD to observe described 200 DEG C × 30 minutes copper foil surfaces after heat treatment after electrolytic polishing, the crystal orientation of plane roll is 30～70% with the area occupation ratio that the differential seat angle in [100] orientation is crystal grain more than 15 degree.

3. rolling Copper Foil according to claim 1, wherein, after by hot ingot bar rolling, repeat cold rolling and annealing, finally carrying out final cold rolling manufactures, in this final cold rolling operation, the 60 surperficial degree glossiness G60 that measure along rolling parallel direction in the stage before 1 mill train of final mill train_RDExceed 300.

4. according to the rolling Copper Foil described in any one in claim 1～3, contain one or more totals 30～300wtppm selecting from the group of Ag, Sn, In, Au, Pd and Mg.