CN103442818B - Rolled copper foil - Google Patents

Rolled copper foil Download PDF

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Publication number
CN103442818B
CN103442818B CN201280015838.7A CN201280015838A CN103442818B CN 103442818 B CN103442818 B CN 103442818B CN 201280015838 A CN201280015838 A CN 201280015838A CN 103442818 B CN103442818 B CN 103442818B
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copper foil
rolling
thickness
shear band
cold rolling
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CN103442818A (en
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中室嘉一郎
千叶喜宽
大久保光浩
鲛岛大辅
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JX Nippon Mining and Metals Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metal Rolling (AREA)

Abstract

[problem] provides and makes copper foil surface moderately coarse and the good rolled copper foil of etching characteristic that is difficult to produce scar, surface while improving operability and then bendability excellence, when the operation of Copper Foil on surface.[solution] rolled copper foil, its surface roughness Ra, be more than 0.004 with the ratio R a/t of the thickness t of Copper Foil and less than 0.007, use FIB to make along the length of the rolling parallel direction of Copper Foil to be the cross section of 25 μm, when observing the scanning ion microscope image in this cross section, the mean value Lsa of the arrival degree of depth Ls of the shear band on the thickness direction of Copper Foil, relative to the thickness t of Copper Foil, the relation of satisfied 0.01≤Lsa/t≤0.4.

Description

Rolled copper foil
Technical field
The present invention relates to the rolled copper foil being suitable for requiring in the FPC of bendability.
Background technology
The Copper Foil used in bending FPC (flexible printed circuit board) requires high bendability.As the method for giving Copper Foil bendability, the technology (patent document 1) of the degree of orientation of the crystal orientation in (200) face of known raising Copper Foil, being increased in the technology (patent document 2) of the ratio of the crystal grain that the thickness of slab direction of Copper Foil is run through, the surface roughness Ry (maximum height) being equivalent to the degree of depth in oil hole of Copper Foil being reduced to the technology (patent document 3) of less than 2.0 μm.
Common FPC manufacturing step is as described below.First Copper Foil is engaged with resin molding.For joint, there is the method by carrying out imidizate to the varnish applying heat treatment be coated on Copper Foil, by the resin molding method of carrying out lamination overlapping with Copper Foil with bonding agent.The Copper Foil with resin molding engaged by these steps is called CCL (copper clad laminate).By the heat treatment in this CCL manufacturing step, Copper Foil recrystallization.
But, when using Copper Foil to manufacture FPC, if raising and the adaptation of cover layer and etch copper foil surface, then likely produce the depression (dish-like sagging) that diameter is several about 10 μm on the surface.Think that its reason is, when crystal orientation is controlled in (200) face by the mode of cube tissue development after with recrystallization annealing, whole face is formed as homogeneous etching speed, relative to this, if there is the crystal grain with different grain arrangements partly, then only this part forms the etching speed different from surrounding, compared with surrounding, is formed locally dark depression.This depression becomes to be made the etching of circuit reduce or in visual examination, is judged as bad and yield rate is reduced reason.
As reducing the method for this depression, reporting before the rolling or after rolling, machine glazed finish being carried out to the surface of Copper Foil, after the distortion forming affected layer is provided, carrying out the technology (patent document 4) of recrystallization.According to this technology, after the recrystallization due to affected layer, there is a lot of inhomogenous crystal grain from the teeth outwards, the different crystal grain of crystal orientation can not individualism.
On the other hand, the applicant reports following technology (patent document 5): reducing above-mentioned depression to make copper foil surface moderately level and smooth, preventing from making the copper foil surface too smoothly transverse direction slip etc. produced when leading to paper tinsel simultaneously, and make the surface roughness Ra s of rolling vertical direction larger than the surface roughness Ra p of rolling parallel direction.
Prior art document
Patent document
Patent document 1: patent No. 3009383 publication
Patent document 2: Japanese Unexamined Patent Publication 2006-117977 publication
Patent document 3: Japanese Unexamined Patent Publication 2001-058203 publication
Patent document 4: Japanese Unexamined Patent Publication 2009-280855 publication
Patent document 5: Japanese Unexamined Patent Publication 2010-227971 publication.
Summary of the invention
But, patent document 4 record technology when, because inhomogenous crystal grain is many, not along (200) planar orientation, therefore there is the problem that bendability reduces in the crystallization of copper foil surface.
On the other hand, although in order to ensure when the manufacture of Copper Foil and the adaptation of roller or make the operation of Copper Foil goods become easy, and carry out making final cold rolling time the roughness of roller become process that is large, that make copper foil surface become coarse, if but make copper foil surface coarse, then the degree of orientation of the crystallization of copper foil surface reduces, and bendability is poor or be easy to produce dish-like sinking.Therefore, in above-mentioned patent document 5, describe to make copper foil surface moderately level and smooth, and the surface roughness Ra roll of the Rolling roller in finally cold rolling is set to 0.05 ~ 0.15 μm, and make its oil film equivalent be less than the paragraph 0014 of 30000(patent document 5).But, when judging by this manufacture method manufacturing copper foil, when this operation, be easy to produce scar (" reference example " with reference in following embodiment) on surface.
Namely, the present invention is the invention made to solve above-mentioned problem, even if its object is to provide making copper foil surface moderately coarse to improve operability, also can not make bendability deterioration and being difficult to produce the good rolled copper foil of etching characteristic on scar, surface on surface.
The present inventor etc. have carried out various research, found that: the rough surface (such as by the rolling system that roughness is low) not too making Copper Foil before finally cold rolling final passage, and in finally cold rolling final passage, make the rough surface of Copper Foil (such as by coarse rolling system, namely, in finally cold rolling final passage, with the roughness changing Rolling roller before it), even if make the rough surface of final Copper Foil thus, shear band also can not arrive too dark at the thickness direction of Copper Foil, dish-like sinking can be reduced when not making bendability deterioration, and when the operation of Copper Foil, be difficult on surface produce scar.
To achieve these goals, for rolled copper foil of the present invention, at copper foil surface, in rolling parallel direction, length is 175 μm of surface roughness Ra measured, be more than 0.004 with the ratio R a/t of the thickness t of above-mentioned Copper Foil and less than 0.007, use FIB, making along the length of the rolling parallel direction of above-mentioned Copper Foil is the cross section of 25 μm, when observing the scanning ion microscope image in this cross section, the mean value Lsa of the arrival degree of depth Ls of the shear band on the thickness direction of above-mentioned Copper Foil, relative to the thickness t of above-mentioned Copper Foil, meet the relation of 0.01≤Lsa/t≤0.4.
200 DEG C of heating 30 minutes and under the modified state being recrystallized structure, the intensity (I in (200) face that the intensity (I) in (200) face of being tried to achieve by the X-ray diffraction of rolling surface is tried to achieve relative to the X-ray diffraction by micro mist copper 0) be I/I 0>=50, it is 175 μm in above-mentioned copper foil surface length in rolling parallel direction, and be separated by 3 straight lines of more than 50 μm in rolling vertical direction respectively, be equivalent to the maximum height of thickness direction of each straight line and the mean value d of the difference of minimum constructive height of the depth capacity in oil hole, and the ratio d/t of the thickness t of above-mentioned Copper Foil is preferably less than 0.1.
After the copper foil surface electrobrightening further after heat treatment in 200 DEG C × 30 minutes, when utilizing EBSD to observe, the area occupation ratio being the crystal grain of more than 15 degree from the differential seat angle in [100] orientation is preferably less than 20%.Should illustrate, here so-called " further through heat treatment in 200 DEG C × 30 minutes " refer to be subject in claim 2 200 DEG C carry out 30 minutes heating thermal history time, heat treatment again.
After ingot bar hot rolling, cold rolling and annealing are being carried out, in the final cold rolling step after more than 1 time, preferably making the surface roughness of the Rolling roller before final passage more level and smooth than the surface roughness of the Rolling roller of final passage repeatedly.Wherein, the surface roughness of Rolling roller is the center line average roughness specified in JISB0601.
After ingot bar hot rolling, repeatedly carrying out in the final cold rolling step after more than 1 time by cold rolling and annealing, in the stage preferably before final passage, Ra/t is more than 0.002 and less than 0.004.
According to the present invention, can obtain making copper foil surface moderately coarse and while improving operability and then bendability excellence, when the operation of Copper Foil on surface, be difficult to produce the good rolled copper foil of etching characteristic on scar, surface.
The simple declaration of accompanying drawing
[Fig. 1] shows the roughness of copper foil surface, the figure with the relation of shear band.
[Fig. 2] display is along the ideograph of the tissue in the cross section of the rolling parallel direction of Copper Foil.
[Fig. 3] display is equivalent to the figure of the assay method of the mean value d of the depth capacity in oil hole.
[Fig. 4] shows the figure of the optical microscope image of embodiment 1.
[Fig. 5] shows the figure of the optical microscope image of comparative example 3.
[Fig. 6] shows the figure of the EBSD measurement result of embodiment 1.
[Fig. 7] shows the figure of the EBSD measurement result of comparative example 3.
[Fig. 8] shows the figure of the section S IM image of the Copper Foil sample of embodiment 2.
[Fig. 9] shows the figure of the section S IM image of the Copper Foil sample of comparative example 3.
[Figure 10] shows the figure of the section S IM image of the Copper Foil sample of comparative example 6.
[Figure 11] shows the figure of bend test method.
Detailed description of the invention
Below the rolled copper foil of embodiments of the present invention is described.Should illustrate, in the present invention, % only otherwise special instruction, then represents quality %.
First with reference to Fig. 1, technological thought of the present invention is described.If increase finally cold rolling in the roughness of roller make copper foil surface coarse, then the operability of Copper Foil improves, but easily produces and dish-likely sink (past case 1 of Fig. 1).
The reason of known dish-like sagging generation is, by cold rolling with coarse roller and import concavo-convex at copper foil surface, and then shear band is expanded dearly in a thickness direction.That is, by recrystallization annealing crystallization control orientation, during to make cube tissue development, the shear band extended becomes the starting point of the crystal grain with the grain arrangement different from local around.And, because this crystal grain has the etching speed different from other crystal grain, if therefore etched, then compared with surrounding, dark depression can be formed locally.
The mechanism that the shear band extended makes the crystal grain with the grain arrangement different from local around produce as described below.
First, be out of shape due to the slip distortion of crystallization although add the material being subject to shearing force man-hour in the rolling of material, if rolling processing is in progress and makes strain increase, then only utilize slip distortion not to be out of shape, cause material deformation by detrusion.This shearing (distortion) band is owing to shearing crystal grain, thus at shear band, crystal grain is divided.Further, shear band causes strain by the tissue that have accumulated, and the driving force therefore generating new crystal grain when recrystallization annealing is high.Therefore think when annealing, even if in the crystal grain around shear band, (200) face is expanded, and also generates the crystal grain with random orientation in shear band.As shear band, strain is made the degree of orientation in material monolithic (200) face reduce by the tissue that have accumulated compared with the tissue of surrounding, therefore not preferred.
Should illustrate, shear band is the tissue sheared by crystal grain, when from during along the cross-section of rolling parallel direction, is cut off continuously by crystal grain in a thickness direction with prescribed depth, and at the end of shear band, crystal grain is cut-off and remain in a thickness direction.In the present invention, described in specific as follows, use FIB(FIB) make above-mentioned cross section, observe the SIM(scanning ion microscope in this cross section) image, differentiate shear band.
Here, mainly concavo-convex (depression, the oil hole etc.) of copper foil surface become starting point and form shear band, and when Copper Foil is subject to shearing force, the above-mentioned concavo-convex bottleneck becoming material deformation, produces distortion with this as the starting point, is easy to form detrusion.Therefore, there is following situation: even if at the comparatively initial stage of rolling, so concavo-convex immediately below depth direction on shear band also expand.
Thus, there will be a known the bendability in order to obtain Copper Foil all the time and reduce the method for surface roughness.Think this is because undertaken finally cold rolling by the roller low by roughness, make the concavo-convex minimizing on the surface of the generation starting point becoming shear band, the thickness direction of Copper Foil is difficult to produce shear band.But when reducing the surface roughness of Copper Foil, the operability of Copper Foil reduces (past case 2 of Fig. 1).
According to the above, the present inventor finds by finally cold rolling final passage and the surface roughness changing Rolling roller before it, namely before finally cold rolling final passage, not too make the rough surface (such as by the rolling system that roughness is low) of Copper Foil, and in finally cold rolling final passage, make the rough surface (such as by coarse rolling system) of Copper Foil, even if make the rough surface of final Copper Foil, also expanding of shear band can be suppressed, dish-like sinking tails off, and when the operation of Copper Foil, be difficult on surface produce scar (the present invention's example of Fig. 1).
Namely, in the past, the orientation of Copper Foil is considered to the roughness depending on copper foil surface simply, but in fact not only the roughness on surface has impact, and the scale (divergence) of the shear band of material internal more can have impact to the degree of orientation (sinking with dish-like).And in finally cold rolling, if can material surface roughness be suppressed to be level and smooth fully in the passage before final passage, even if then make in final passage, copper foil surface is coarse carries out fine finishining, also can obtain high orientation.
Here, dish-like sagging number may not be relevant to surface roughness.This is because copper foil surface concavo-convex immediately below not certainly exist shear band (with reference to figure 8).Therefore, the concavo-convex degree of depth self of copper foil surface does not determine the divergence of shear band.But when carrying out that finally surface roughness that is cold rolling, that make Copper Foil diminishes with the roller that roughness is low as mentioned above, because the divergence of shear band is suppressed, therefore to have to a certain degree relevant for surface roughness and dish-like sagging number.
But, in the present invention, in order to make copper foil surface moderately coarse, needing to control (regulation) shear band itself, and being not the surface roughness of Copper Foil.
Therefore, the present inventor, according to following index, by directly specifying the degree of expansion of shear band, successfully making the bendability of the Copper Foil with the coarse surface of appropriateness improve, suppressing dish-like sagging generation and suppressing to produce scar when the operation of Copper Foil on surface.
(1) degree of expansion of shear band
As the index of the degree of expansion of shear band, as shown in Figure 2, at the mean value Lsa of the arrival degree of depth Ls of the shear band of the thickness direction of Copper Foil relative to the thickness t of Copper Foil, the relation of 0.01≤Lsa/t≤0.4 is met.Should illustrate, be set to Lsa (mm)/t (mm).
Fig. 2 is that length is 25 μm and the ideograph of tissue along the cross section of this rolling parallel direction on the rolling parallel direction RD of Copper Foil.Copper foil surface 2a forms 3 concavo-convex 4, and at these in concavo-convex 4, immediately below 2 of outside are concavo-convex, shear band 10 extends in a thickness direction.Wherein, symbol G represents crystal grain, and crystal grain G is the region fenced up with grain circle GB.Shear band 10 cuts off crystal grain in a thickness direction continuously, by the end not having grain circle of cut-off crystal grain to be set to shear band, the degree of depth from the thickness of slab direction of copper foil surface 2a to end is defined as the arrival degree of depth Ls of shear band.
Should illustrate, P 1represent that crystal grain is sheared the part that band 10 cuts off, grain circle GB offsets.In addition, P 2represent that crystal grain is not sheared the part that band 10 cuts off, grain circle GB does not offset, and become the position of the end of shear band.Like this, the Ls equalization of each shear band observed in a visual field, 1 shown in Fig. 2 is tried to achieve Lsa, will similarly observe the cross section in 3 visuals field and the mean value of the Lsa obtained respectively adopts as Lsa.
Should illustrate, there is following characteristics: 1) shear band is immediately below concavo-convex, 2) shear band is almost straight line, can not in midway bending or bending, once interrupt, then can not again occur, 3) when faces different for the contrast of crystal grain is set to interface, shear band or grain boundary can be observed at interface on metal structure is observed.
Shear band is from the different of grain boundary, and the grain boundary of rolling stock is that the mode of surrounding a crystal grain exists, in contrast, shear band is then the straight line cutting off multiple crystal grain continuously, and exists at a certain angle relative to rolling parallel direction.In addition, when being difficult to distinguish from the end of the straight line of concavo-convex extension, the point that the cut-out of crystal grain can be stopped, namely encountering contrast is that a kind of point of crystal grain is set to end.
In addition, as the method for the relation of satisfied 0.01≤Lsa/t≤0.4, not too make the rough surface of Copper Foil (be such as that roller that the roughness of such as less than 0.05 μm low be rolled by surface roughness Ra) before can being set forth in finally cold rolling final passage, and in finally cold rolling final passage, make the rough surface of Copper Foil (being such as rolled with the coarse roller that surface roughness Ra is such as more than 0.06 μm).
During recrystallization annealing, around shear band, be easy to the crystal grain that generation is difficult to unanimously have from the crystal orientation in (200) face the orientation different with the orientation in (200) face, but the easiness occurred is relevant with the arrival degree of depth Ls of shear band.Therefore, by controlling in the mode of the relation meeting 0.01≤Lsa/t≤0.4, the degree of depth of shear band shoals on the whole, and the generation with the crystal grain in the orientation different from the orientation in (200) face is suppressed, and dish-like sinking tails off.On the other hand, when Lsa/t > 0.4, shear band deepens, and the crystal grain with the orientation different from the orientation in (200) face generates in a large number, produces multiple dish-like sagging.
Should illustrate, as Lsa/t, be set to the ratio relative to thickness of slab t, this is because the impact of the shear band degree of depth is different according to thickness of slab.In addition, Lsa/t is more little more preferred, but angularly considers from the manufacturing condition of the practicality of Copper Foil, makes the lower limit of Lsa/t be set to 0.01.
In the present invention, use FIB to make the cross section of Copper Foil, observe the scanning ion microscope image in this cross section, judge the arrival degree of depth Ls of shear band.
FIB(FIB) can fine processing be carried out, smooth cross section can be obtained.In addition, SIM(scanning ion microscope) secondary electron that image discharges when being and utilizing FIB scanned sample, contrast grow compared with SEM image of composition or crystal orientation, therefore can differentiate the crystal grain that be sheared band and cut off in precision highland.As the FIB for making cross section, Ga+ ion beam can be used.
In addition, in the present invention, 2 adjacent areas with the poor contrast obtained by SIM image are considered as different crystal grain respectively, their border is considered as a boundary.Then, the part that grain circle immediately below concavo-convex 4 of copper foil surface 2a offsets in RD direction is considered as shear band 10, this skew connects by the thickness direction of Copper Foil.The position of the skew not observing the RD direction on a boundary is set to the end P of shear band 2, will from copper foil surface 2a to P 2till the distance of thickness direction be set to Ls.
Fig. 8 ~ Figure 10 represents the section S IM image of the Copper Foil sample of following embodiment and comparative example.In fig. 8, known in 4 concavo-convex 4, there is the situation that shear band 10 extends immediately below concavo-convex, and do not produce the situation of shear band immediately below concavo-convex.In addition, by the poor contrast of section S IM image, the part (shear band) that grain circle immediately below concavo-convex 4 offsets in RD direction can be differentiated.
Should illustrate, in the cross-sectional image of above-mentioned Fig. 8, drawing tangent line L to 2 teats surrounding the depression A sunk from copper foil surface 2a from left and right, is that more than 0.1 μm person is set to concavo-convex 4 by the distance of the thickness direction of L and A.
Then, for rolled copper foil of the present invention other regulation and composition be described.
（2）Ra/t
In order to make copper foil surface moderately coarse, reduce dish-like sinking, using as the thickness t(mm of the surface roughness Ra (mm) after finally cold rolling with Copper Foil simultaneously) the Ra/t of value of ratio be defined as more than 0.004 and less than 0.007.So, surface roughness can be made identical with Copper Foil in the past, reduce dish-like sinking simultaneously.Should illustrate, by by surface roughness divided by thickness, no matter the thickness of Copper Foil can how carry out the evaluation of the roughness of copper foil surface.On the other hand, if Ra/t is less than 0.004, then copper foil surface too becomes level and smooth, when the operation of Copper Foil, is easy to produce scar on surface.If Ra/t is more than 0.007, then copper foil surface is too thicker, and the degree of orientation of the crystallization of copper foil surface reduces, and bendability is poor, or is easy to produce dish-like sinking.
Wherein, surface roughness Ra (center line average roughness) specifies according to JIS B0601, in the present invention, it is set to and is 175 μm and the mean value of the value that 3 straight lines of more than 50 μm of being separated by respectively in rolling vertical direction measure in copper foil surface length in rolling parallel direction.In addition, in the present invention, surface roughness can use contact surface roughmeter (little slope studies made SE-3400) to measure.Should illustrate, the surface roughness of copper foil surface and Rolling roller is all set to above-mentioned center line average roughness.
（3）d/t
Even if consider that the roughness of copper foil surface is not the shear band in too large, most oil hole when not having anything expand, sometimes also there is several oil deeply and cheat.In dark oil hole, the possibility of shear band expansion is high, and in this case, it becomes the starting point of dish-like sagging generation.Therefore, in the present invention, the mean value d(mm of the depth capacity of oil being cheated) be defined as d/t≤0.1.
The mean value d(mm of depth capacity by oil is cheated) divided by thickness t(mm), no matter the thickness of Copper Foil can how carry out the evaluation of copper foil surface.That is, even if this is because the depth capacity in oil hole is identical, if the thickness t(mm of Copper Foil) thinning, then its impact also becomes large.
At this, the mean value d(mm of depth capacity in oil hole) refer to as shown in Figure 3 on surfaces of the copper foil on rolling parallel direction RD length be 175 μm and the 3 straight line L of more than 50 μm of being separated by respectively on rolling vertical direction TD 1~ L 3on, be equivalent to each straight line L of the depth capacity in oil hole 1~ L 3the maximum height H of thickness direction mwith minimum constructive height H sdifference di(mm) mean value.Specifically, with contact roughness, measure L 1~ L 3on the distribution of thickness direction obtain maximum height H mand minimum constructive height H (mm) s(mm), by each straight line L 1~ L 3di on average.
Should illustrate, comparative example 2 described as follows is such, even if d/t≤0.1, also has and dish-like sagging situation occurs.
The thickness of Copper Foil (or copper alloy foil) has no particular limits, such as, can be applicable to the Copper Foil (or copper alloy foil) of use 5 ~ 50 μm.
（4）I/I 0
In order to give Copper Foil height bendability of the present invention, with 200 DEG C of heating 30 minutes and modified under the state of recrystallized structure, the intensity (I in (200) face that the intensity (I) in (200) face of being tried to achieve by the X-ray diffraction by rolling surface is tried to achieve relative to the X-ray diffraction by micro mist copper 0) be defined as I/I 0≤ 50.Thus, the degree of orientation in (200) face of bendability excellence improves.I/I 0during < 50, bendability reduces.Above-mentioned is imitate the temperature experience of giving Copper Foil in CCL manufacturing step 200 DEG C of annealing carried out 30 minutes.Should illustrate, I/I 0as long as the determinator of the general X-ray diffraction of value just can measure.Such as RINT2500(Co., Ltd. リ ガ Network system can be used) measure.In addition, as long as x-ray source uses generally by the element (such as Cu, Co etc.) used.
Should illustrate, in order to make I/I 0≤ 50, preferably finally cold rolling degree of finish is more than 90%, is more preferably more than 95%.In addition, and then preferably finally cold rolling degree of finish is more than 98%.
(5) make use of the gun parallax of EBSD
Heat 30 minutes and modified under the state of recrystallized structure at 200 DEG C, by when observing with EBSD after copper foil surface electrobrightening, the area occupation ratio being preferably the crystal grain of more than 15 degree from the differential seat angle in [100] orientation is less than 20%.Above-mentioned is imitate the temperature experience of giving Copper Foil in CCL manufacturing step 200 DEG C of annealing carried out 30 minutes.Should illustrate, to the Copper Foil becoming the CCL receiving thermal history, also can heat 30 minutes at 200 DEG C.Heat treatment, until the material of primary recrystallization, even if heat on this, also has almost no change again, and when therefore observing with EBSD, does not distinguish the Copper Foil receiving thermal history and the Copper Foil do not accepted, and heats 30 minutes at 200 DEG C.
When observing with EBSD, if above-mentioned area occupation ratio is less than 20%, the gun parallax that then crystal grain of copper foil surface is mutual is little, the ratio that the crystal grain that crystal orientation is different in uniform tissue exists individually tails off, therefore reduce by etching the depression (dish-like sagging) caused, and then when the operation of Copper Foil, be difficult on surface produce scar.Should illustrate, when utilizing EBSD to observe, 20% is less than for making above-mentioned area occupation ratio, can be rolled at the following roller of final cold rolling middle use as mentioned above, described roller makes the roller that in the passage of material surface roughness fully smoothly, namely before finally cold rolling final passage, roughness (surface roughness Ra is such as less than 0.05 μm) is less in the passage before final passage.
(6) form
As Copper Foil, can use the tough pitch copper of purity more than 99.9%, oxygen-free copper, in addition, as copper alloy foil, intensity as requested, electric conductivity can use known copper alloy.As known copper alloy, the copper alloy being such as mixed with 0.004 ~ 0.3% tin, the copper alloy being mixed with 0.004 ~ 0.05% silver medal can be enumerated, contain by the copper alloy etc. of more than one in the element that In, Zn, Zr, Ti, Fe, P, Ni, Si, Sn, Ag, Te, Cr, Nb, V are formed to add up to 0.004 ~ 0.5%, wherein, as the material of excellent electric conductivity, preferably use the copper that with the addition of 0.02% silver medal.
Like this, rolled copper foil of the present invention except the such fine copper system of tough pitch copper, oxygen-free copper, the alloy also containing above-mentioned composition.
Then, an example of the manufacture method of rolled copper foil of the present invention is described.First, by the alloying element of copper and needs so that comprise inevitable impurity ingot bar hot rolling after, cold rolling and annealing is repeatedly finally specific thickness in final cold rolling middle fine finishining.
At this, as mentioned above, by not too making the rough surface of Copper Foil before finally cold rolling final passage, and in finally cold rolling final passage, make the surface of Copper Foil roughening, form the surface state with the oil hole making the rough surface of final Copper Foil but be difficult to expand to shear band thus, dish-like sinking tails off.Further, the area occupation ratio in the oil hole on the surface that this shear band is few is more than 6 and less than 15%.
Therefore, before finally cold rolling final passage, in order to not too make the rough surface of Copper Foil, roughness (surface roughness Ra is such as less than 0.05 μm) smaller roller can be used to be rolled, or increase finally cold rolling in 1 passage degree of finish be rolled.On the other hand, in finally cold rolling final passage, use roughness (surface roughness Ra is such as more than 0.06 μm) larger roller to be rolled, or use the high ROLLING OIL of viscosity to be rolled, make the copper foil surface of final gained coarse.
Should illustrate, in order to improve the surface state with the oil hole making the rough surface of final Copper Foil but be difficult to expand to shear band, in finally cold rolling final 2 passages or final passage, as mentioned above, need to use coarse roller or use the high ROLLING OIL of viscosity to be rolled, but be easy to aspect from adjustment, the rolling condition preferably in the final passage of adjustment.On the other hand, if by roughening for the roughness of roller before finally cold rolling final 3 passages, then in the oil hole formed and then by the processing of final passage, shear band is expanded.
Should illustrate, adjustable annealing conditions, be 5 ~ 20 μm to make by the average grain diameter of the recrystallization grain of the annealing gained just before finally cold rolling.In addition, can make finally cold rolling in rolling degree of finish be more than 90%.
Embodiment
Ingot casting is cast as raw material using the copper of composition table 1 Suo Shi or copper alloy, hot rolling is carried out until thickness is 10mm more than 800 DEG C, after the oxide skin of effects on surface carries out flush cut, cold rolling and annealing repeatedly, being finally refined to thickness in finally cold rolling is 0.009 ~ 0.018mm.Make finally cold rolling in rolling degree of finish be 95 ~ 99.8%.Should illustrate, in table 1, tough pitch copper is recited as TPC, oxygen-free copper is recited as OFC.Oxygen-free copper is at JIS-H0500(C1011) in the oxygen-free copper of regulatory specifications, tough pitch copper is at JIS-H0500(C1100) in the tough pitch copper of regulatory specifications.
Should illustrate, finally cold rollingly to carry out with 10 ~ 15 passages, as shown in table 1, the surface roughness of the surface roughness of the roller till changing before final passage and the roller of final passage is rolled.Identical from the surface roughness of the roller of the 1st passage to before final passage of final rolling.
In addition, as " reference example 6 ~ 9 ", according to the manufacture method of patent document 5, before the final passage of final cold rolling step and in final passage, make that the surface roughness of Rolling roller is identical makes Copper Foil sample.Should illustrate, reference example 6 ~ 9 corresponds respectively to the table 1 of embodiment 4,1,3,6(with reference to patent document 5 of patent document 5).
To each Copper Foil sample obtained like this, carry out the evaluation of each characteristic.
(1) shear band
Use FIB (FIB), as shown in Figure 2, the length made along the rolling parallel direction RD of Copper Foil is the cross section of 100 μm, observes the scanning ion microscope image in this cross section.By in above-mentioned cross section, using the length along RD be 25 μm as 1 visual field, observe 4 visuals field.Shear band Pan Do method is as illustrated in fig. 2.FIB device uses the goods name " NVision40 " of エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd..
(2) cube set tissue
After sample is heated 30 minutes at 200 DEG C, try to achieve the integrated value (I) of (200) face intensity of being tried to achieve by the X-ray diffraction of rolling surface.By this value divided by the integrated value (I of (200) face intensity measuring the micro mist copper (heat at 300 DEG C after 1 hour in 325 orders, hydrogen stream and use) obtained in advance 0), calculate I/I 0value.
(3) depth capacity (mean value d) in oil hole
Use Laser Scanning Confocal Microscope (レ ー ザ ー テ ッ Network Inc., model: HD100D), as shown in Figure 3, try to achieve respectively on surfaces of the copper foil, length is 175 μm and the 3 straight line L of more than 50 μm of being separated by respectively on rolling vertical direction TD on rolling parallel direction RD 1~ L 3on maximum height H mwith minimum constructive height H spoor di.By each straight line L 1~ L 3di average and obtain d.And, obtain d (mm)/t (mm).
(4) make use of the gun parallax of EBSD
For the specimen surface after heating in (2), with EBSD (EBSD device, Jeol Ltd. JXA8500F, accelerating potential 20kV, electric current 2 × 10 after electrobrightening -8a, measurement range 1000 μm × 1000 μm, stride 5 μm) observe.Being tried to achieve from the differential seat angle in [100] orientation by graphical analysis is the area occupation ratio of the crystal grain of more than 15 degree.Then for the sample containing this range of observation, use ア デ カ テ ッ Network CL-8 (Co., Ltd. ア デ カ system) 20% solution, carry out the etching of 2 minutes at normal temperatures, light and shade binaryzation is carried out to the image obtained by the surface optics microscope photographing after etching, the dark portion of minor axis more than 50 μm is counted as dish-like sinking.Should illustrate, the copper foil surface after etching forms the shape of reflection crystal orientation, has the face that the organization formation in [100] orientation is parallel with copper foil surface, in contrast, the concavo-convex of crystal orientation appears resulting from the part with other crystal orientation.Therefore, dark dish-like sagging part is seen with light microscope.
Should illustrate, Fig. 4 represents the optical microscope image of embodiment 1, and Fig. 5 represents the optical microscope image of comparative example 3.In addition, Fig. 6 represents the EBSD measurement result of embodiment 1, and Fig. 7 represents the EBSD measurement result of comparative example 3.In Fig. 6, Fig. 7, the region representation of grey or black is the crystal grain of more than 15 degree from the differential seat angle in [100] orientation.
(5) scar on surface
The surface of visual each sample, by length be in the rolling direction more than 10mm scar there is 5 places/m 2above situation conduct ×.
(6) bendability
Sample is heated at 200 DEG C after within 30 minutes, carrying out recrystallization, by the bend test device shown in Figure 11, carry out the mensuration of flexible life.This device is formed as the structure in conjunction with vibration transfer member 3 on vibratory drive body 4, tested Copper Foil 1 the part of screw 2 shown in arrow and the leading section of 3 totally 4 be fixed on device.If vibration section about 3 drives, then the pars intermedia of Copper Foil 1 bends to hair clip (hairpin) shape with the radius of curvature r of regulation.In this test, until the number of times of fracture when obtaining repeated flex under the following conditions.
Should illustrate, experimental condition is as described below: test film width: 12.7mm, test film length: 200mm, test film gather direction: the length direction of test film parallelly with rolling direction is gathered, the thickness t of radius of curvature r:1.0mm(Copper Foil is the situation of 0.009mm), the thickness t of radius of curvature r:1.5mm(Copper Foil is the situation of 0.012mm), the thickness t of radius of curvature r:2.5mm(Copper Foil is the situation of 0.018mm), vibrating stroke: 25mm, vibration velocity: 1500 beats/min.
Should illustrate, when flexible life is more than 20,000 times, being set to and having excellent bendability, is be evaluated as ◎ more than 50,000 times by flexible life, flexible life is more than 20,000 times and is less than 50,000 times to be evaluated as zero, flexible life is less than be evaluated as 20,000 times ×.
(7) surface roughness (Ry) of the copper foil surface after etching
For following comparative example 2,6, in order to effect clearly of the present invention, following method is utilized to measure the surface roughness (Ry) of the copper foil surface after etching.
By the sodium persulfate aqueous solution of temperature 50 C, concentration 100g/L with the pressure injection of 2kg/cm2 on specimen surface, carry out in the depth direction about 9 μm reduction etching.Then, according to JISB0601, use contact roughmeter to try to achieve the maximum height (Ry) on surface.Datum length is set to 0.8mm, the direction parallel with rolling direction measures.The mensuration of Ry changes position and carries out 5 times, tries to achieve the maximum of the measured value of 5 times.
The result of gained is shown in table 1, table 2.
[table 1]
[table 2]
From table 1, table 2, when the Ra/t of end article be more than 0.004 and less than 0.007 and each embodiment of Lsa/t≤0.4, dish-like sagging number is few, and then does not have scar at copper foil surface, and bendability is also excellent.In addition, when each embodiment, what utilize EBSD to obtain is the crystal grain of more than 15 degree from the differential seat angle in [100] orientation area occupation ratio is less than 20%.
On the other hand, surface roughness for the roller making finally cold rolling whole passages (containing final passage) is the situation of the comparative example 1 of less than Ra=0.04 μm, because the Ra/t of final passage is less than 0.004, therefore at copper foil surface with scar, operability is poor.
For in finally cold rolling, the surface roughness of the roller till making before final passage is coarse to more than Ra=0.06 μm, the situation that makes the surface roughness of the roller of final passage be the comparative example 2 of less than Ra=0.05 μm, because the Ra/t of end article is less than 0.004, thus at copper foil surface with scar, operability is poor.In addition, owing to using coarse roller before final passage, thus copper foil surface before final passage is roughening, even if the roller using roughness little in final passage, shear band is also formed.Therefore, d/t is less than 0.1, but the value of Lsa/t is more than 0.4.Consequently from the differential seat angle in [100] orientation be the area occupation ratio of the crystal grain of more than 15 degree more than 20%, produce multiple dish-likely to sink.
In addition, for the situation of comparative example 2, the surface roughness (Ry) of the copper foil surface after etching is 1.51 μm.It can thus be appreciated that, even if the value of Ry is little, also has and produce multiple dish-like sagging situation.
For in finally cold rolling, the situation of the surface roughness of roller till making before final passage and all coarse comparative example 3,4,5 to more than Ra=0.06 μm of the surface roughness of the roller of final passage, when Ra/t before 1 passage of final passage is more than 0.004, copper foil surface becomes coarse, after final passage, shear band is expanded.Therefore, Lsa/t, more than 0.4, produces multiple dish-like sagging.In addition, the differential seat angle in [100] orientation is that the area occupation ratio of the crystal grain of more than 15 degree is more than 20% certainly.
Should illustrate, for the situation of comparative example 3,4, owing to making the roll surface roughness of finally cold rolling whole passages become coarse, thus produce at material internal the oil hole that multiple shear band significantly extends.Therefore, not only Lsa/t is more than 0.4, and the degree of orientation of the crystallization of copper foil surface reduces, I/I 0< 50.Correspondingly, the differential seat angle in [100] orientation is that the area occupation ratio of the crystal grain of more than 15 degree is more than 20% certainly.On the other hand, for the situation of comparative example 5, because the roughness of the roller till making before final passage is comparatively level and smooth compared with comparative example 3,4, thus I/I 0be more than 50, be value high compared with comparative example 3,4, bendability is good.
In addition, the surface roughness (Ry) of the copper foil surface after the etching of comparative example 5 is 2.49 μm.
Fig. 8 ~ Figure 10 represents the section S IM image of the Copper Foil sample of embodiment 2, comparative example 3, comparative example 6 respectively.Known immediately below concavo-convex 4, shear band 10 extends.In addition, the known poor contrast by section S IM image, can differentiate the part (shear band) that grain circle immediately below concavo-convex 4 offsets in RD direction.Further, with embodiment 2(Fig. 8) compared with, the dark shear band 10 of comparative example 3,4 is more, and the value of Lsa/t also becomes large.
Should illustrate, the symbol (a) of Fig. 8 ~ Figure 10 represents section S IM image itself, and the shear band 10 that symbol (b) has represented Pan Do is presented at the symbol on section S IM image.
In addition, for before the final passage of final cold rolling step and in final passage, make the situation of the reference example 6 ~ 9 that the surface roughness of Rolling roller is identical, all produce multiple dish-like sagging, the scar on surface is remarkable simultaneously, and operability is poor.
Should illustrate, for the situation of reference example 6, before the final passage of final cold rolling step and in final passage, the surface roughness of Rolling roller is smoothly (Ra=0.05 μm), therefore Lsa/t is less than 0.4, but Ra/t is less than 0.004, and the scar on surface is remarkable.
On the other hand, for the situation of reference example 7 ~ 9, before the final passage of final cold rolling step and in final passage, the surface roughness of Rolling roller is all coarse (Ra is more than 0.05 μm), and therefore Lsa/t is more than 0.4, and the scar on surface is remarkable.

Claims (5)

1. rolled copper foil, its when copper foil surface, in rolling parallel direction, length is 175 μm measure surface roughness Ra, be more than 0.004 with the ratio R a/t of the thickness t of above-mentioned Copper Foil and less than 0.007, and the thickness t of above-mentioned Copper Foil is 5 ~ 50 μm,
Use FIB, making along the length of the rolling parallel direction of above-mentioned Copper Foil is the cross section of 25 μm, when observing the scanning ion microscope image in this cross section, the mean value Lsa of the arrival degree of depth Ls of the shear band on the thickness direction of above-mentioned Copper Foil, relative to the thickness t of above-mentioned Copper Foil, the relation of satisfied 0.01≤Lsa/t≤0.4.
2. rolled copper foil according to claim 1, wherein, 200 DEG C of heating 30 minutes and under the modified state being recrystallized structure, the intensity I in (200) face that the intensity I in (200) face of being tried to achieve by the X-ray diffraction of rolling surface is tried to achieve relative to the X-ray diffraction by micro mist copper 0for I/I 0>=50,
Be 175 μm in above-mentioned copper foil surface length in rolling parallel direction and be separated by 3 straight lines of more than 50 μm in rolling vertical direction respectively, being equivalent to the maximum height of thickness direction of each straight line and the mean value d of the difference of minimum constructive height of the depth capacity in oil hole, is less than 0.1 with the ratio d/t of the thickness t of above-mentioned Copper Foil.
3. rolled copper foil according to claim 1 and 2, wherein, after the copper foil surface electrobrightening further after heat treatment in 200 DEG C × 30 minutes, when utilizing EBSD to observe, the area occupation ratio being the crystal grain of more than 15 degree from the differential seat angle in [100] orientation is less than 20%.
4. rolled copper foil according to claim 1 and 2, wherein, after ingot bar hot rolling, cold rolling and annealing are being carried out, in the final cold rolling step after more than 1 time, making the surface roughness of the Rolling roller before final passage more level and smooth than the surface roughness of the Rolling roller of final passage repeatedly.
5. rolled copper foil according to claim 1 and 2, wherein, after ingot bar hot rolling, repeatedly carrying out in the final cold rolling step after more than 1 time by cold rolling and annealing, in the stage before final passage, Ra/t is more than 0.002 and less than 0.004.
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