CN102573287B - Rolled copper foil - Google Patents

Rolled copper foil Download PDF

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CN102573287B
CN102573287B CN201110333742.2A CN201110333742A CN102573287B CN 102573287 B CN102573287 B CN 102573287B CN 201110333742 A CN201110333742 A CN 201110333742A CN 102573287 B CN102573287 B CN 102573287B
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copper foil
pit
rolling
final
cold rolling
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CN102573287A (en
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千叶喜宽
中室嘉一郎
大久保光浩
鲛岛大辅
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JX Nippon Mining and Metals Corp
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    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/18—Polishing of light metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • B21B2003/005—Copper or its alloys

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metal Rolling (AREA)

Abstract

A rolled copper foil is provided to improve the treating efficiency, flexibility, and surface etching property thereof. In a rolled copper foil, the ratio between a surface roughness, which is measured at 175[mu]m in a rolled direction, and a thickness is 0.004-0.007. When the rolled copper film is heated for 30 minutes at 200[deg.]C, the ratio between a surface strength (I0) of the rolled surface obtained by X-ray diffraction and the strength of pulverized copper powder obtained by X-ray diffraction is equal to or greater than 50. On three straight lines that are separated 50[mu]m or more in a vertical direction to the rolled direction, the ratio between the average height of the lines in a thickness direction and the thickness of the copper film is 0.1 or less. In the process of detection through using a confocal microscopy, the area rate of a recess is 6%-15%.

Description

Rolled copper foil
Technical field
The present invention relates to be applicable to require the rolled copper foil of the FPC of bendability.
Background technology
The crooked Copper Foil with use in FPC (flexible printed circuit board) requires high bendability.As making Copper Foil there is the method for bendability, the technology (patent documentation 1) of the degree of orientation of the crystal orientation of (200) face of known raising Copper Foil, increase the thickness of slab direction that connects Copper Foil crystal grain ratio technology (patent documentation 2), by Copper Foil be equivalent to pit ( ) the surface roughness Ry (maximum height) of the degree of depth be reduced to the technology (patent documentation 3) below 2.0 μ m.
Common FPC manufacturing step is as described below.First Copper Foil is engaged with resin molding.Joint has by the varnish being coated on Copper Foil is applied to the method that imidizate is carried out in heat treatment, by the resin molding with bonding agent and the overlapping method of carrying out lamination of Copper Foil.The Copper Foil with resin molding engaging by these steps is called CCL (copper clad laminate).By the heat treatment in this CCL manufacturing step, Copper Foil recrystallization.
But, while using Copper Foil to manufacture FPC, if raising with the adaptation of coverlay, copper foil surface is carried out to etching, on surface, likely producing diameter is the depression (dish-like sinking) of several 10 μ m left and right, particularly the easy high crooked Copper Foil of generation.Its reason is, in order to give high bendability, the crystal orientation of Copper Foil (200) face is controlled to such an extent that unanimously make to produce cube tissue after full annealed.In other words, even if think and carry out this control, crystal orientation that also can be inwhole is all consistent, the local different crystal grain of crystal orientation that exists in the tissue of homogeneous.Now, different according to the different etching speeds of etched crystal face, so this crystal grain etched must with compare local deeply around, form depression.This depression causes the etching of circuit to reduce, or in visual examination, is judged as bad and yield reduces.
As the method that reduces this depression, reported before rolling or after rolling mechanical polishing has been carried out in the surface of Copper Foil, provide after the distortion that forms affected layer, the technology (patent documentation 4) of recrystallization.According to this technology, owing to there being from the teeth outwards a lot of inhomogenous crystal grain after affected layer recrystallization, the different crystal grain of crystal orientation is individualism not.
[prior art document]
[patent documentation]
No. 3009383 communique of [patent documentation 1] 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
But in the situation of the technology that patent documentation 4 is recorded, because inhomogenous crystal grain is many, not along (200) planar orientation, therefore there is the problem of bendability reduction in the crystallization of copper foil surface.
On the other hand, the Copper Foil of the high glaze that patent documentation 3 is recorded, crystal orientation is easily consistent, and in addition, dish-like sagging generation is also few.But, the surface of the Copper Foil of high glaze easily produce cut ( ) etc., operation is not easy, so not preferred.
Therefore, the present invention proposes in order to address the above problem, and its object is, by making copper foil surface moderately form coarse state, provides that operability is good, bendability is excellent time, the rolled copper foil that surface etching characteristic is good.
The inventor has carried out various research, found that, in final cold rolling final passage (パ ス), do not make before the surface of Copper Foil too coarse, in final cold rolling final passage, make the rough surface of Copper Foil, make thus the shaggy while of final Copper Foil, the form of pit and frequency (surface state) are difficult for producing shear band, and bendability is excellent, dish-like sagging minimizing simultaneously.And the form and the frequency (surface state) that are difficult for the pit of generation shear band can be carried out the evaluation in macroscopic view by the pit area occupation ratio being obtained by confocal images.
In order to reach above-mentioned purpose, rolled copper foil of the present invention, on copper foil surface, along the ratio R a/t that measures the thickness t of the surface roughness Ra that obtains and above-mentioned Copper Foil in 175 μ m length of the direction parallel with rolling direction, be 0.004～0.007, at 200 ℃, heat under the state of 30 minutes modified crystalline structures of attaching most importance to, the intensity (I) of (200) face of being tried to achieve by the X-ray diffraction of rolling surface, with respect to the intensity (I of (200) face of being tried to achieve by the X-ray diffraction of micropowder copper 0), be I/I 0>=50, on copper foil surface along the direction length parallel with rolling direction be 175 μ m and with the rectangular direction of rolling direction on respectively on 3 more than 50 μ m straight lines of distance, be equivalent to the maximum height of thickness direction of each straight line of depth capacity of pit and the ratio d/t of the thickness t of the mean value d of the difference of minimum constructive height and above-mentioned Copper Foil is below 0.1, the area occupation ratio of the pit while measuring with Laser Scanning Confocal Microscope is 6%～15%.
By after the copper foil surface electrobrightening after heat treatment in above-mentioned 200 ℃ * 30 minutes, while observing with EBSD, with the differential seat angle of [100] orientation be that the area occupation ratio of crystal grain more than 15 degree is preferably below 20%.
Preferably ingot bar is carried out after hot rolling, repeat cold rolling and annealing, finally carry out final cold rolling manufacture, in this final cold rolling process, in the stage before final passage, Ra/t is 0.002～0.004.
According to the present invention, make the coarse operability that improves of copper foil surface appropriateness, the good rolled copper foil of surface etching characteristic when obtaining bendability excellence.
Accompanying drawing explanation
[Fig. 1] is for representing the figure of the roughness of copper foil surface and the relation of detrusion band.
[Fig. 2] is for illustrating the figure of pit shape.
[Fig. 3] is for illustrating the figure of assay method of the mean value d of the depth capacity that is equivalent to pit.
[Fig. 4] is for illustrating the figure of the surperficial optical microscope image of embodiment 1.
[Fig. 5] is for illustrating the figure of the surperficial optical microscope image of comparative example 1.
[Fig. 6] is for illustrating the figure of the confocal images of embodiment 1.
[Fig. 7] is for illustrating the figure of the confocal images of comparative example 1.
[Fig. 8] is for illustrating the figure that measures the method for flexible life by bend test device.
Embodiment
Below the rolled copper foil of embodiments of the present invention is described.In the present invention, % only otherwise special instruction represents quality %.
First with reference to Fig. 1, technological thought of the present invention is described.If increase the roughness of final cold rolling central roll, make copper foil surface coarse, the operability of Copper Foil improves, but easily produces dish-like sink (past case 1 of Fig. 1).This thinks as described below.
By final matte roll in cold rolling, on the surface of Copper Foil, form pit, along with the carrying out of processing, easily the top ends at pit produces detrusion band.If further continue, process detrusion band to depth development.So, produce the part of pit of dark detrusion band when recrystallization, in other the tissue of homogeneous, become the different crystal grain of crystal orientation, the dish-like sagging starting point while becoming etching.
On the other hand, be known as so far the bendability that obtains Copper Foil and the method that improves glossiness (surface roughness).Think this be due to, finally cold rolling by utilizing roller that roughness is low to carry out, suppress the formation of pit, thereby be difficult for producing detrusion band.But if improve the glossiness (reducing surface roughness) of Copper Foil, the operability due to Copper Foil reduces (past case 2 of Fig. 1), from the viewpoint of utilizing Copper Foil not preferred.
On the other hand, the inventor finds, before final cold rolling final passage, do not make the surface of Copper Foil too coarse (for example, by the low rolling system of roughness), in final cold rolling final passage, make the rough surface (being for example rolled with coarse roller) of Copper Foil, form thus pit, the surface of final Copper Foil forms coarse state, but form shape and the frequency of the pit that not too produces detrusion band, the different crystal grain of result crystal orientation in the tissue of homogeneous reduces, dish-like sagging minimizing (inventive example of Fig. 1).
In other words, thought that the orientation of Copper Foil only depended on the roughness of copper foil surface, but the scale (formation degree) of the detrusion band of in fact known material internal there is impact to the degree of orientation (and dish-like sinking) in the past.And, if final cold rolling in, in the passage before final passage, can suppress fully the formation of shear band, even if be processed into coarse copper foil surface in final passage, also can obtain high orientation.
In addition, the invention is characterized in, the area occupation ratio by the pit that obtained by confocal images carries out macroscopic evaluation to the degree of formation of above-mentioned shear band, finds out the scope of the area occupation ratio of dish-like sagging reduction.
On the other hand, while only utilizing the value of the surface roughness of using so far, can not grasp clearly the information of pit.In other words, if observe rolled copper foil surface, along observing the generation of pit with the rectangular direction TD of rolling direction, known as shown in Figure 2, the cross sectional shape of pit, except there is the short leg-of-mutton pit (the symbol P1 of Fig. 2) of the length of TD direction, also has trapezoidal pit (the symbol P2 of Fig. 2).In addition,, even if the degree of depth of pit is identical, also there are the wide shape of the degree of expansion of cheating and narrow shape in RD direction.Think and in the mensuration of the surface roughnesses such as the common Ra, the Ry that measure the surface undulation of Copper Foil, Rz, Sm, can not reflect fully the difference of the shape of these pits.
Therefore, use Laser Scanning Confocal Microscope, obtain the ratio (area occupation ratio) of the image-region that is equivalent to pit, reflect thus the shape of pit, can obtain corresponding to dish-likely sinking, the fine or not difference of bendability.And, for the area occupation ratio of pit, by take difference in height binaryzation before and after the threshold value of regulation of the Z axis (short transverse) obtaining with Laser Scanning Confocal Microscope, the part darker than this threshold value extracted out as pit portion, obtain its area ratio.
Then the regulation of rolled copper foil of the present invention and composition are described.
(1) area occupation ratio of pit
As mentioned above, before final cold rolling final passage, do not make the surface of Copper Foil too coarse, in final cold rolling final passage, make the rough surface of Copper Foil, make thus the shaggy while of final Copper Foil, obtain the difficult shape that forms the pit of detrusion band, dish-like sagging minimizing.And there is the surface of the pit of this difficult formation detrusion band, known by the inventor's experiment (embodiment described later), the area occupation ratio of the pit while measuring with Laser Scanning Confocal Microscope is 6%～15%.
If the area occupation ratio of pit surpasses 15%, the pit that forms detrusion band increases.If form detrusion band at material internal,, when recrystallization, in other homogeneous tissue, form the different crystal grain of crystal orientation, dish-like the sinking while easily producing etching.
On the other hand, the situation that is less than 6% as the area occupation ratio of pit, has 2 conditions.Condition 1 is used the roller that roughness is low in final cold rolling whole passages.Under this condition, because dark pit is few, be difficult for forming detrusion band, dish-like sagging minimizing, but the surface roughness of Copper Foil too small (not meeting the condition of Ra/t described later) has difficulties in the operating aspect of Copper Foil goods, so not preferred.
Second condition made the rough surface of Copper Foil before final cold rolling final passage, in final cold rolling final passage, used the low roller of roughness to make the surface smoothing of Copper Foil.Under this condition, by using the low roller of roughness in final passage, the part that approaches copper foil surface before final passage in the pit that makes to form approaches smooth in final passage expansion, and surface roughness reduces.But the narrow paddy part of pit inside is still residual.Therefore, the opening of the surface part of pit narrows down and the area occupation ratio of pit itself reduces, but owing to using coarse roller before final passage, forms detrusion band in pit, and residual detrusion band after final passage, produces many dish-like sagging.Although and but so the area occupation ratio of pit is little produces many dish-like sagging states become remarkable when the area occupation ratio of pit is less than 6%.
And, as the area occupation ratio that makes pit, it is more than 6% method, as mentioned above, can final cold rolling in, to form the mode of pit in shallow, the pit that do not form shear band in the passage before final passage, in passage before final cold rolling final passage, use the smaller roller of roughness (surface roughness Ra is for example that 0.05 μ m is following) to be rolled, and in final cold rolling final passage, use the larger roller of roughness (surface roughness Ra is for example more than 0.06 μ m) to be rolled, make the copper foil surface that finally obtains coarse.Pit that passage before final passage forms is shallow, do not form shear band, and therefore, in final cold rolling final passage, even if make the rough surface of Copper Foil, the pit that forms shear band can not increase yet, dish-like sagging minimizing.On the other hand, if in the passage before final cold rolling final passage, use the large roller of roughness (surface roughness Ra for example surpasses 0.05 μ m) to be rolled, form the pit that easily forms shear band, in final passage, form pit, its area change, the area occupation ratio of pit surpasses 15%, the formation of shear band becomes significantly, easily produces dish-like sinking.
Wherein, in final cold rolling step, in the passage before final passage, use the smaller roller of roughness (surface roughness Ra is for example that 0.05 μ m is following), make thus final cold rolling copper foil surface smoother.Specifically, in the stage before a time of the final passage of final cold rolling process, making the ratio (Ra/t) of surface roughness Ra and paper tinsel thickness t is 0.0020～0.0040.If the surface state based on Ra/t within the scope of this is carried out the rolling of final passage, even if make the rough surface of Copper Foil in final passage, be also difficult for importing shear band in formed pit, so preferably.
And as described later, (Ra/t) after the final passage of final cold rolling process finishes is 0.004～0.007.
(2)?I/I 0
In order to give high bendability to Copper Foil of the present invention, at 200 ℃, heat under the state of 30 minutes modified crystalline structures of attaching most importance to, the intensity (I) of (200) face of being tried to achieve by the X-ray diffraction of rolling surface, with respect to the intensity (I of (200) face of being tried to achieve by the X-ray diffraction of micropowder copper 0), stipulate as I/I 0>=50.Thus, the degree of orientation of (200) face of bendability excellence improves.If I/I 0< 50, and bendability reduces.The temperature history of in the annealing of 30 minutes simulation CCL manufacturing process, Copper Foil being given at above-mentioned 200 ℃.
And, in order to make I/I 0>=50, preferably final cold rolling degree of finish is more than 98%.
(3)?Ra/t
In order surface roughness to be compared reduce steadily dish-like sinking with surface roughness in the past, final Ra (the mm)/t (mm) after cold rolling of regulation is 0.004～0.007.Surface roughness is identical with Copper Foil in the past if so, meanwhile, can reduce dish-like sinking.And, by using surface roughness divided by thickness, can independently to the roughness of copper foil surface, evaluate with the thickness of Copper Foil.For example, if the thickness t attenuation of Copper Foil, even if be identical surface roughness, concave-convex surface shared ratio in copper thickness increases, and likely can not by the area occupation ratio of above-mentioned pit, evaluate copper foil surface fully.
Wherein, Ra (center line average roughness) is stipulated by JIS B0601, in the present invention, on copper foil surface along the direction length parallel with rolling direction be 175 μ m and with the rectangular direction of rolling direction on measure respectively the mean value of the value obtaining on 3 more than 50 μ m straight lines of distance.
(4)?d/t
Even think in so not large, the most of pit of roughness of copper foil surface and how not form in the situation of detrusion band, also likely have some dark pits.The possibility that forms detrusion band in dark pit is high, in this case, becomes the starting point of dish-like sagging generation.Therefore,, in the present invention, the mean value d of the depth capacity of pit regulation is d/t≤0.1.
By with the mean value d of the depth capacity of pit divided by thickness t, can independently to copper foil surface, evaluate with the thickness of Copper Foil.That is, even if this is because the depth capacity of pit is identical, if its impact increase of the thickness t attenuation of Copper Foil.
Wherein, the mean value d of the depth capacity of pit, as shown in Figure 3, on copper foil surface on the direction RD parallel with rolling direction length be 175 μ m and with the rectangular direction TD of rolling direction on 3 more than 50 μ m straight line L of distance respectively 1～L 3above, each straight line L that is equivalent to the depth capacity of pit 1～L 3the maximum height H of thickness direction mwith minimum constructive height H sthe mean value of poor di.Specifically, with contact roughness, measure L 1～L 3on the profile of thickness direction, obtain maximum height H mwith minimum constructive height H s, by each straight line L 1～L 3di on average.
To the thickness of Copper Foil (or copper alloy foil) without particular limitation of, for example can use suitably the Copper Foil of 5～50 μ m.
(5) misorientation obtaining by EBSD
As mentioned above, in the dish-like tissue sinking for the heat treatment when Copper Foil is engaged with resin molding, homogeneous that recrystallization obtains, when the ratio of the crystal grain individualism that crystal orientation is different is many, when etching, this independent crystal grain is etched must be than the dark and depression that forms around.Wherein, as above-mentioned heat treatment, the heat-treat condition of the temperature history of Copper Foil being given in CCL manufacturing process in simulation (at 200 ℃ 30 minutes) the modified crystalline structure of attaching most importance to of lower heating Copper Foil.And as the crystal orientation of this state, while observing copper foil surface with EBSD after electrobrightening, being preferably crystal grain more than 15 degree with the differential seat angle of [100] orientation, area occupation ratio is below 20%.And, for be subject to whole thermal histories formation the Copper Foil of CCL, also can at 200 ℃, heat 30 minutes.Be heat-treated to the Copper Foil of recrystallization, even if further heating also can change hardly, in the observation of therefore observing by EBSD, do not distinguish and stood the Copper Foil of thermal history, the Copper Foil of not subjected course, and at 200 ℃, heat 30 minutes.
If above-mentioned area occupation ratio is less than 20% while observing by EBSD, the misorientation of the intergranule of copper foil surface is little, in homogeneous tissue, the ratio of the different crystal grain individualism of crystal orientation reduces, and the depression therefore forming due to etching (dish-like sinking) reduces.And, in order to make above-mentioned area occupation ratio be less than 20% when observing by EBSD, can be as mentioned above final cold rolling in, in passage before final passage, suppress the formation of shear band, in other words, in passage before final cold rolling final passage, use the smaller roller of roughness (surface roughness Ra is for example that 0.05 μ m is following) to be rolled.
(6) form
As Copper Foil, can use purity for tough pitch copper more than 99.9wt%, oxygen-free copper, also can use known copper alloy according to desired intensity, conductivity in addition.
Oxygen-free copper is by JIS-H3510 (alloy sequence number C1011), JIS-H3100 (alloy sequence number C1020) standardization, and tough pitch copper is by JIS-H3100 (alloy sequence number C1100) standardization.
As known copper alloy, can enumerate the copper alloy (being more preferably added with the copper alloy of the tin of 0.001～0.02wt%) of the tin that is for example added with 0.01～0.3wt%; Be added with the silver-colored copper alloy of 0.01～0.05wt%; Be added with the copper alloy of the indium of 0.005～0.02wt%; Be added with the copper alloy of the chromium of 0.005～0.02wt%; Contain and be selected from more than one in tin, silver, indium and chromium and amount to copper alloy below 0.05wt% etc., wherein, as the copper alloy of excellent electric conductivity, usually use Cu-0.02wt%Ag.
Then an example of the manufacture method of rolled copper foil of the present invention is described.First, by after the ingot bar hot rolling that comprises copper and necessary alloying element and inevitable impurity, repeat cold rolling and annealing, finally final, be processed as specific thickness in cold rolling.
Wherein, as mentioned above, before final cold rolling final passage, do not make the surface of Copper Foil too coarse, in final cold rolling final passage, make the rough surface of Copper Foil, make thus the rough surface of final Copper Foil, but form the surface state with the pit that is not easy to produce detrusion band, dish-like sagging minimizing.And, the few surface of this detrusion band, the area occupation ratio of pit is 6%～15%.
Therefore, can be before final cold rolling final passage, so that the not too coarse mode of copper foil surface, use the smaller roller of roughness (surface roughness Ra is for example that 0.05 μ m is following) to be rolled or increase final a second processing degree in cold rolling to be rolled.On the other hand, in final cold rolling final passage, use the rolling system that roughness (surface roughness Ra is for example more than 0.06 μ m) is larger or use the high ROLLING OIL of viscosity to be rolled, making the copper foil surface that finally obtains coarse.
And, in order to manufacture the surface state that final copper foil surface is coarse, still have the pit that is difficult for formation detrusion band, in final cold rolling final two passages or final passage, must use as mentioned above coarse roller or use the high ROLLING OIL of viscosity to be rolled, but from the viewpoint of easy adjustment, preferably adjust the rolling condition of final passage.On the other hand, if made the roughness of roller coarse before final cold rolling final three passages, in formed pit, further the processing due to final passage forms detrusion band.
And can adjusting annealing conditions, to make by being about to carry out the average grain diameter of the recrystallization grain that final annealing before cold rolling obtains be 5～20 μ m.In addition it is more than 98%, can making final cold rolling rolling degree of finish.
[embodiment]
To be added with the tough pitch copper of element of the composition shown in table 1 or oxygen-free copper as raw material, casting ingot, carries out hot rolling until thickness is 10mm at 800 ℃, above by after surperficial oxidation scale facing cut, repeat cold rolling and annealing, finally at the final thickness of recording in being processed as table 1 in cold rolling.Final cold rolling rolling degree of finish is 99.2%.
And " the adding the TPC of 0.02%Ag " on the hurdle of the composition of table 1 refers to the Ag of the middle 0.02 quality % of interpolation of tough pitch copper (TPC) of JIS-H3100 (alloy sequence number C1100).In addition, " the adding the OFC of 0.01%Ag, 0.005%Sn " on the composition hurdle of table 1 refers in the oxygen-free copper (OFC) of JIS-H3100 (alloy sequence number C1020) and adds the Ag of 0.01 quality % and the Sn of 0.005 quality %.Wherein, only in embodiment 6, as oxygen-free copper, use is by JIS-H3510 (alloy sequence number C1011) standardized oxygen-free copper (OFC), in embodiment 4,5,8,9, as oxygen-free copper, use by JIS-H3100 (alloy sequence number C1020) standardized oxygen-free copper (OFC).
And, final cold rolling 10～15 passages of carrying out, as shown in table 1, change until the surface roughness of the surface roughness of the roller before final passage and the roller of final passage is rolled.Final passage from the first passage until to carry out the surface roughness of the roller before final passage all identical.And the degree of finish of final rolling is 99% except comparative example 5, comparative example 5 is 96%.
For each Copper Foil sample so obtaining, various characteristics is evaluated.
(1) surface roughness Ra: Ra (center line average roughness) measures according to JIS B0601, for use Laser Scanning Confocal Microscope (レ ーザ ーテック society system, model: HD100D), measure the value obtaining in 175 μ m length of the direction parallel with rolling direction for sample surfaces.
(2) cube set tissue
Sample is heated after 30 minutes at 200 ℃, try to achieve the integrated value (I) of (200) the face intensity of trying to achieve with the X-ray diffraction of rolling surface.By this value divided by the integrated value (I that measures in advance (200) face intensity of the micropowder copper obtain (heat in 325 orders, hydrogen stream 1 hour then use) at 300 ℃ 0), calculate I/I 0value.
(3) depth capacity of pit (mean value d)
Use Laser Scanning Confocal Microscope (レ ーザ ーテック society system, model: HD100D), as shown in Figure 3, try to achieve respectively direction RD length parallel with rolling direction on copper foil surface be 175 μ m and with the rectangular direction TD of rolling direction on 3 more than 50 μ m straight line L of distance respectively 1～L 3on maximum height H mwith minimum constructive height H spoor di.By each straight line L 1～L 3di on average obtain d.And, obtain d (mm)/t (mm).
(4) misorientation obtaining by EBSD
For heat the sample surfaces after 30 minutes in (2) at 200 ℃, after electrobrightening, with EBSD (Electron Back-Scattered Diffraction device, the JXA8500F of Jeol Ltd., accelerating voltage 20kV, electric current 2e-8A, measurement range 1000 μ m * 1000 μ m, stride 5 μ m), observe.By graphical analysis, trying to achieve with the differential seat angle of [100] orientation is the area occupation ratio of crystal grain more than 15 degree.Further, in the square range of observation of sample surfaces 1mm, the visual number that crystallization particle diameter is surpassed to the crystal grain of 20 μ m is counted.Then for the sample that contains this range of observation, use ア デ カ テ ッ Network CL-8 (the ア デ カ of Co., Ltd. system) 20% solution, carry out at normal temperatures etching in 2 minutes, the image that surface after etching is obtained with optics microscope photographing is carried out to light and shade binaryzation, and the dark portion that minor axis is surpassed to 50 μ m is as dish-like sagging counting.And the copper foil surface after etching forms the shape of reflection crystal orientation, the tissue with [100] orientation forms the face parallel with copper foil surface, and the concavo-convex of crystal orientation appears resulting from the part on the other hand with other crystal orientation.Therefore, with light microscope, see dark dish-like sagging part.
And Fig. 4 represents the surperficial optical microscope image of embodiment 1, Fig. 5 represents the surface optical MIcrosope image of comparative example 3.
(4) area occupation ratio of pit
For sample surfaces, by Laser Scanning Confocal Microscope (レ ーザ ーテック society system, model: HD100D) the mensuration visual field of 300 * 300 μ m is measured.In measuring the visual field, make sample move up in optical axis (Z axis) side, obtain the image (this is called FMS (Focus Scan Memory) image) apart from the copper foil surface 10nm degree of depth.Then, regard the part darker than 10nm apart from copper foil surface as pit, carry out 2 value processing.The example of this image is Fig. 6 and Fig. 7, and light tone is partly pit.Then for measuring the visual field 300 * 300 μ m, for the area (area of light tone) of pit, use commercially available image processing software to try to achieve area, calculate the area occupation ratio of pit.
(5) surface cut ( )
The surface of visual each sample, in rolling direction length be more than 10mm cut be 5 places/m 2situation conduct *.
(6) bendability
Sample is heated at 200 ℃ and within 30 minutes, carry out, after recrystallization, by the bend test device shown in Fig. 8, carrying out the mensuration of flexible life.This device is formed on vibratory drive body 4 in conjunction with the structure of vibration transmission member 3, tested Copper Foil 1 by the leading section of the part of the screw 2 shown in arrow and 3 totally 4 be fixed on device.If vibration section 3 drives up and down, the pars intermedia of Copper Foil 1 bends to hair clip (hair pin) shape with the radius of curvature r of regulation.In this test, while obtaining under following condition repeated flex until the number of times of fracture.
And, when thickness of slab is 0.012mm, experimental condition is as described below: test film width: 12.7mm, test film length: 200mm, test film are taked direction: make that the length direction of test film parallelly with rolling direction is taked, radius of curvature r:2.5mm, vibrating stroke: 25mm, vibration velocity: 1500 beats/min.Flexible life is for 30,000 times when above, is judged as and has excellent bendability.
In addition, when each thickness of slab is 0.018mm, 0.006mm, for making the bend test of the situation that flexural deformation is 0.012mm with thickness of slab identical, radius of curvature is changed to respectively to 4mm, 1.3mm, other experimental condition is identical.
Resulting result is as shown in table 1.
As shown in Table 1, I/I 0>=50, d/t be below 0.1 and the situation of the area occupation ratio of pit each embodiment that is 6%～15% under, the differential seat angle with [100] orientation obtaining by EBSD is that the area occupation ratio of crystal grain more than 15 degree is less than 20%, dish-like sagging number is few, and copper foil surface no marking, bendability is also excellent.In addition,, in the situation of each embodiment, the Ra/t of end article is 0.004～0.007.
On the other hand, the surface roughness of the roller of final cold rolling whole passages (comprising final passage) is all in the situation of the comparative example 1,5 below Ra=0.04 μ m, and the Ra/t of final passage is less than 0.004, and the area occupation ratio of pit is less than 6%, therefore at copper foil surface, form cut, operability variation.
And in the situation of comparative example 5, surface roughness is little, the area occupation ratio of pit is less than 6%, and still final cold rolling rolling degree of finish reduces, is 96%, so I/I 0< 50, and the formation degree of orientation is low, the inconsistent state of crystal orientation.When crystal orientation is inconsistent, mean that having a lot of differential seat angles that are orientated with [100] is crystal grain more than 15 degree, the area occupation ratio of this crystal grain surpasses 20%, therefore produces many dish-like sinking.
Final cold rolling in, make the surface roughness of the roller before final passage coarse, more than Ra=0.06 μ m, the surface roughness of the roller of final passage is that in the situation of the comparative example 2 below Ra=0.05 μ m, the Ra/t of end article is less than 0.004, therefore copper foil surface forms cut, operability variation.In addition, owing to using coarse roller before final passage, therefore in pit, form detrusion band, even if use also residual detrusion band of roller that roughness is little in final passage, therefore the area occupation ratio of pit is less than 6%, and being crystal grain more than 15 degree with the differential seat angle of [100] orientation, area occupation ratio surpasses 20%.Result produces many dish-like sinking.
Final cold rolling in, in the situation that until the surface roughness of the roller of the surface roughness of the roller before final passage and final passage all coarse, be comparative example 3,4,6 more than Ra=0.06 μ m, Ra/t before a time of final passage is more than 0.004, before final passage, produce the pit of many formation detrusion bands.Therefore, final passage recurve pit area rate surpasses 15%, and the area occupation ratio that is crystal grain more than 15 degree with the differential seat angle of [100] orientation surpasses 20%.Result produces many dish-like sinking.
And in the situation of comparative example 3,4, owing to making, the roll surface roughness of final cold rolling whole passages is coarse, therefore produces the pit of many remarkable formation detrusion bands at material internal.Therefore, not only pit area occupation ratio surpasses 15%, and the reduction of the degree of orientation of the crystallization of copper foil surface, I/I 0< 50.Correspondingly, being crystal grain more than 15 degree with the differential seat angle of [100] orientation, area occupation ratio surpasses 20%.On the other hand, in the situation of comparative example 6, until the roughness ratio comparative example 3,4 of the roller before final passage is smooth, so I/I 0being more than 50, is the value higher than comparative example 3,4, and bendability is good.

Claims (3)

1. rolled copper foil, wherein, on copper foil surface, along the ratio R a/t that measures the thickness t of the surface roughness Ra that obtains and described Copper Foil in 175 μ m length of the direction parallel with rolling direction, be 0.004～0.007, at 200 ℃, heat under the state of 30 minutes modified crystalline structures of attaching most importance to, the intensity I of (200) face of being tried to achieve by the X-ray diffraction of rolling surface is with respect to the intensity I of (200) face of being tried to achieve by the X-ray diffraction of micropowder copper 0, be I/I 0>=50,
On copper foil surface along the direction length parallel with rolling direction be 175 μ m and with the rectangular direction of rolling direction on respectively on 3 more than 50 μ m straight lines of distance, be equivalent to the maximum height of thickness direction of each straight line of depth capacity of pit and the ratio d/t of the thickness t of the mean value d of the difference of minimum constructive height and described Copper Foil is below 0.1
The area occupation ratio of the pit while measuring with Laser Scanning Confocal Microscope is 6%～15%.
2. rolled copper foil as claimed in claim 1, wherein, by after the copper foil surface electrobrightening after heat treatment in described 200 ℃ * 30 minutes, while observing with EBSD, the area occupation ratio that is crystal grain more than 15 degree with the differential seat angle of [100] orientation is below 20%.
3. rolled copper foil as claimed in claim 1 or 2, wherein, carries out after hot rolling ingot bar, repeats cold rolling and annealing, finally carries out final cold rolling manufacture, and in this final cold rolling process, in the stage before final passage, Ra/t is 0.002～0.004.
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