CN103118812B - Rolled copper foil - Google Patents

Rolled copper foil Download PDF

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Publication number
CN103118812B
CN103118812B CN201180046620.3A CN201180046620A CN103118812B CN 103118812 B CN103118812 B CN 103118812B CN 201180046620 A CN201180046620 A CN 201180046620A CN 103118812 B CN103118812 B CN 103118812B
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copper foil
rolling
glossiness
degree
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CN103118812A (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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    • 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
    • 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
    • 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
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

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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)
  • Microelectronics & Electronic Packaging (AREA)
  • Metal Rolling (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

The invention provides a rolled copper foil, of which the surface is roughened adequately so as to improve the handling properties of the foil, and which has excellent flexibility and good surface etching properties. [Solution] A rolled copper foil; in which the surface has a 60 DEG glossiness (G60RD) of 100 to 300 inclusive as measured in the direction parallel to the direction of rolling in accordance with JIS-Z8741; the intensity (I) of face (200) in a rolled surface as determined by X-ray diffraction is a value represented by the following formula: I/I0 = 50 wherein I0 represents the intensity of face (200) in a fine copper powder as determined by X-ray diffraction and wherein the intensities are determined in such a state where the copper foil is heated at 200 DEG C for 30 minutes to convert the structure of the copper foil into a recrystallized structure; the ratio (d/t) is 0.1 or less in three straight lines that are located on the surface of the copper foil in the direction parallel to the direction of rolling, have lengths of 175 [mu]m and are separated at least 50 [mu]m away from one another in the direction perpendicular to the direction of rolling, wherein 'd ' represents the average value of the differences each between the maximum height and the minimum height in the thickness-wise direction in each of the lines, and wherein the difference corresponds to the maximum depth of an oil pit in the individual lines, and 't ' represents the thickness of the copper foil; and the ratio (G60RD/G60TD) of the surface glossiness (G60RD) as measured in the direction parallel to the direction of rolling to the surface 60 DEG glossiness (G60TD) as measured in the direction perpendicular to the direction of rolling is less than 0.8.

Description

Rolled copper foil
Technical field
The present invention relates to the rolled copper foil of the FPC being applicable to require flexibility.
Background technology
Use FPC(flexible printed wiring board to for bending) Copper Foil require high flexibility.As the method for giving Copper Foil flexibility, there will be a known the technology (patent document 1) of the degree of orientation in the crystal orientation in (200) face of improving Copper Foil, make the technology (patent document 2) of the increasing proportion of the crystal grain in the thickness of slab direction of through Copper Foil, the surface roughness Ry(maximum height of the degree of depth being equivalent to oil hole (oil pit) of Copper Foil) be reduced to the technology (patent document 3) of less than 2.0 μm.
Common FPC manufacturing step is as follows.First Copper Foil is engaged with resin molding.In joint, have carry out imidization by applying heat treatment to the varnish coating Copper Foil method, carry out laminated method by with the resin molding of bonding agent and Copper Foil overlap.The Copper Foil with resin molding engaged by these steps is called CCL(copper-clad laminated board).By the heat treatment in this CCL manufacturing step, Copper Foil carries out recrystallization.
But, when using Copper Foil to manufacture FPC, when etching copper foil surface to make to improve with the adaptation of cover layer, produce the depression (dish-like sagging) of diameter number about 10 μm sometimes on surface.Think that its reason is, if be (200) face in the mode of cube tissue growth by crystal orientation control after recrystallization annealing, then in uniform tissue, there is the crystal grain of different crystal orientations individually.And etching speed is different according to etched crystal plane, therefore, this independent crystal grain obtains darker than perimeter etch and forms depression.This depression becomes makes the etching of circuit reduce, or in visual examination, be judged to be bad and productive rate is reduced reason.
As the method reducing this depression, report has following technology: before rolling or after carrying out mechanical lapping on the surface of Copper Foil after rolling and giving the strain becoming processing upgrading layer, carry out recrystallization (patent document 4).According to this technology, the uneven crystal grain that happens suddenly on surface after making recrystallization by processing upgrading layer, then the crystal grain that crystal orientation is different becomes can not individualism.
Prior art document
Patent document
Patent document 1: Japan 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.
Summary of the invention
The technical problem that invention will solve
But the situation of the technology described in patent document 4, uneven crystal grain is many, and the crystallization of copper foil surface is not oriented in (200) face, therefore has the problem that flexibility reduces.
On the other hand, can be judged as guaranteeing the adaptation with roller during manufacturing copper foil, or make the operation of Copper Foil goods become easy, carry out be increase finally cold rolling in roller roughness to make copper foil surface roughening, but when copper foil surface is roughening, the degree of orientation of the crystallization of copper foil surface reduces, and flexibility is deteriorated, or dish-like sinking easily occurs.
That is, the present invention is the invention completed to solve the problems of the technologies described above, and object is to provide and makes copper foil surface moderately roughening, improves operability, and then flexibility is excellent, the rolled copper foil that surface etching characteristic is good simultaneously.
For the method for technical solution problem
The present inventor etc. have carried out various research, found that and do not make the surface of Copper Foil become too coarse before finally cold rolling final rolling pass, and make the surface of Copper Foil become coarse in finally cold rolling final rolling pass, final copper foil surface is made to become coarse thus, make Shear heating instability tail off simultaneously, flexibility is improved, and dish-like sinking tails off.
To achieve these goals, rolled copper foil of the present invention is at 60 degree of glossiness G60 according to JIS-Z8741 on the surface that rolling parallel direction measures rDbe more than 100 and less than 300, under 200 DEG C of heating, 30 minutes modified states 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, copper foil surface in rolling parallel direction length be 175 μm, and be separated by 3 straight lines of more than 50 μm respectively in rolling vertical direction, 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, be less than 0.1 with the ratio d/t of the thickness t of aforementioned Copper Foil, and the 60 degree of glossiness G60 according to JIS-Z8741 on the surface that rolling parallel direction measures rD, and the 60 degree of glossiness G60 according to JIS-Z8741 on the surface that rolling vertical direction measures tDratio G60 rD/ G60 tDbe less than 0.8.
After the copper foil surface electrolytic polishing after heat treatment in above-mentioned 200 DEG C × 30 minutes, when utilizing EBSD to observe, be the area occupation ratio preferably less than 20% of the crystal grain of more than 15 degree from the differential seat angle of [100] orientation.
After ingot bar hot rolling, cold rolling and annealing, finally carries out finally cold rolling and manufactures repeatedly, in this final cold rolling step, in the stage of the last rolling pass of final rolling pass, at 60 degree of glossiness G60 on the surface that rolling parallel direction measures rDbe preferably greater than 300.
Invention effect
According to the present invention, can obtain and make copper foil surface moderately coarse, improve operability, and then flexibility is excellent, and the rolled copper foil that surface etching characteristic is good.
Accompanying drawing explanation
[Fig. 1] shows the figure of the roughness of copper foil surface and the relation of Shear heating instability.
The figure of the relation of [Fig. 2] display oil hole and glossiness.
[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 1.
The figure of the method for measuring of flex fatigue life is carried out in [Fig. 8] display by deflection test setup.
Detailed description of the invention
Below, the rolled copper foil that embodiment of the present invention relates to is described.Should illustrate, as long as no specified otherwise in the present invention, then % represents quality %.
First, with reference to Fig. 1, technological thought of the present invention is described.Make finally cold rolling in roller roughness when becoming large and make copper foil surface roughening, the operability of Copper Foil improves, but flexibility is low, or easily occurs dish-likely to sink (conventional example 1 of Fig. 1).Think that its reason is, by the coarse roller in finally cold rolling, produce Shear heating instability in copper thickness direction, and then continue rolling, Shear heating instability is grown up.
On the other hand, known flexibility in order to obtain Copper Foil and improve the method for glossiness (surface roughness) in the past.Think that its reason is, undertaken finally cold rolling by the roller low by roughness, be difficult to produce Shear heating instability at the thickness direction of Copper Foil.But when making the glossiness of Copper Foil improve (surface roughness diminishes), the operability of Copper Foil reduces (past case 2 of Fig. 1).
On the other hand, the present inventor finds, before finally cold rolling final rolling pass, does not make the surface of Copper Foil too coarse (such as, the roller low by roughness is rolled), in finally cold rolling final rolling pass, the surface of Copper Foil is become coarse (such as, being rolled with coarse roller), thus, the surface of final Copper Foil becomes coarse, Shear heating instability tails off simultaneously, and flexibility is improved, dish-like tail off (the present invention's example of Fig. 1) of sinking.
That is, thought that the orientation of Copper Foil depended on merely the roughness of copper foil surface, but the scale of the Shear heating instability of actual known material internal affects the degree of orientation (sinking with dish-like) in the past always.Further, in finally cold rolling, if the growth of shear band fully can be suppressed in the rolling pass before final rolling pass, though then in final rolling pass by copper foil surface fine finishining cursorily, also can obtain high orientation.
But the one-tenth length of above-mentioned shear band can not only be obtained by the value of the glossiness used in the past clearly.Namely, as shown in " the present invention's example " of Fig. 1, make the surface of final Copper Foil roughening, when making Shear heating instability tail off simultaneously, the then shallow and width had to a certain degree in oil hole, and then the occurrence frequency in oil hole tails off (with reference to Fig. 2 (a)), this is difficult to be embodied in the glossiness of the rolling parallel direction RD vertical with the direction that oil is cheated.On the other hand, from when observing with rolling vertical direction TD, because the width had to a certain degree cheated by oil, therefore shape or the change of frequency of catching oil hole easier than parallel direction.
The relation of this oil hole and glossiness is described with reference to Fig. 2." the present invention's example " of Fig. 2 (a) and (b), (c) difference corresponding diagram 1 is, " past case 1 ", the copper foil surface of " past case 2 ".
First, when " the present invention's example " of Fig. 2 (a), glossiness G is measured along rolling parallel direction rDtime, can not detect that glossiness reduces in the direction change of oil hole reverberation.On the other hand, glossiness G is measured along rolling vertical direction TD tDtime, oily hole extends along TD, and also can detect even if therefore depart from the direction generation horizontal (to RD direction) of oil hole reverberation, glossiness improves.That is, with G rDcompare, G tDrelatively uprise, when measuring 60 degree of glossiness described later, then meet G60 rD/ G60 tDthe relation of < 0.8.
Then, the situation of " past case 1 " of Fig. 2 (b), copper foil surface becomes too coarse, the degree of depth and the length (occurrence frequency) in oil hole increase, even if measure glossiness along either direction in rolling parallel direction RD and rolling vertical direction TD, direction also because of reverberation in oil hole changes and cannot detect, and glossiness reduces.Now, with G rDcompare, G tDrelative step-down, when measuring 60 degree of glossiness described later, then meets G60 rD/ G60 tDthe relation of > 1.
On the other hand, when " past case 2 " of Fig. 2 (c), copper foil surface becomes too level and smooth, and oil hole becomes too shallow, even if therefore measure glossiness G along rolling parallel direction RD rD, in oil hole, the direction of reverberation is also difficult to change, and glossiness improves.That is, with G tDcompare, G rDrelatively uprise, when therefore measuring 60 degree of glossiness described later, then G60 rD/ G60 tDrelation close to 1(namely, the anisotropy of RD and TD diminishes).But, as " past case 1 ", because copper foil surface is not coarse, therefore become G60 rD/ G60 tD< 1.
Next, the regulation of rolled copper foil of the present invention and composition are described.
(1) glossiness G60 rD
Make the 60 ° of glossiness G60 measuring the surface obtained at rolling parallel direction RD rDbe more than 100 and less than 300.G60 rDduring more than 300, then copper foil surface becomes too level and smooth, when Copper Foil manufactures and the adaptation of roller reduce, or the operation of Copper Foil goods has difficulty.On the other hand, G60 rDwhen being less than 100, then copper foil surface becomes too coarse, grows up and the reduction of the degree of orientation of the crystallization of copper foil surface at material internal Shear heating instability, and flexibility is deteriorated, or easily produces dish-like sinking.
（2）G60 RD/G60 TD
As mentioned above, by before finally cold rolling final rolling pass, do not make the surface of Copper Foil too coarse, and make the surface of Copper Foil roughening in finally cold rolling final rolling pass, the surface of Copper Foil final is thus roughening, Shear heating instability tails off simultaneously, and flexibility improves, and dish-like sinking tails off.Further, from the experiment (following embodiment) of the present inventor etc., the surface that this Shear heating instability is few becomes G60 rD/ G60 tD< 0.8.Therefore, regulation rolling parallel direction measures 60 ° of glossiness G60 on the surface obtained rD, and rolling vertical direction measures 60 ° of glossiness G60 on the surface obtained tDratio G60 rD/ G60 tDbe less than 0.8.In addition, employing ratio is the impact in order to offset overall glossiness.
Become G60 rD/ G60 tDwhen>=0.8, then as above-mentioned Fig. 2 (b), copper foil surface becomes too level and smooth, when Copper Foil manufactures and the adaptation of roller reduce, or the operation of Copper Foil goods has difficulty.In addition, as above-mentioned Fig. 2 (c), G60 is become rD/ G60 tDduring > 1, then copper foil surface becomes too coarse, and Shear heating instability is grown up, and flexibility reduces, or easily produces dish-like sinking.
In addition, as making G60 rD/ G60 tDthe method of < 0.8, as described above in finally cold rolling, rolling pass before final rolling pass suppresses the growth of shear band, namely, in the rolling pass before finally cold rolling final rolling pass, roughness (surface roughness Ra is such as less than 0.05 μm) smaller roller is used to be rolled.On the other hand, in finally cold rolling final rolling pass, use roughness (surface roughness Ra is such as more than 0.06 μm) larger roller to be rolled, become coarse to make the copper foil surface of final gained.
At this, in finally cold rolling, in the stage of the last rolling pass of final rolling pass, make the glossiness G60 measuring the surface obtained in rolling parallel direction rDwhen being greater than 300, then, in the rolling pass before finally cold rolling final rolling pass, copper foil surface becomes smoother, and Shear heating instability is difficult to be introduced into, therefore preferably.
（3）d/t
When the thickness t of Copper Foil is thinning, even if identical surface roughness, the ratio of concave-convex surface shared by copper thickness also becomes large, therefore sometimes can not fully carry out utilizing above-mentioned G60 rD/ G60 tDthe evaluation of copper foil surface.Therefore in the present invention by regulation d/t≤0.1, the thickness of Copper Foil can not be relied on to carry out the evaluation of copper foil surface.
At this, d refer to as shown in Figure 3 on surfaces of the copper foil in rolling parallel direction RD length be 175 μm, and 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 sthe mean value of difference di.Specifically, utilize contact roughness, measure L 1~ L 3on the distribution of thickness direction obtain maximum height H mwith minimum constructive height H s, by each straight line L 1~ L 3di on average.
The thickness of Copper Foil (or copper alloy foil) has no particular limits, such as, can be applicable to use 5 ~ 50 μm of persons.
（4）I／I 0
At 200 DEG C heat 30 minutes modified under the state of recrystallized structure, specify the intensity (I in (200) face that the intensity (I) in (200) face obtained by the X-ray diffraction of rolling surface is obtained relative to the X-ray diffraction by micro mist copper 0) be I/I 0>=50.Thus, the degree of orientation in (200) face of flexibility excellence improves.Become I/I 0during < 50, flexibility reduces.Above-mentioned 200 DEG C of annealing of 30 minutes are the temperature experience of imitating to give Copper Foil in CCL manufacturing step.
(5) misorientation of EBSD is utilized
Heat at 200 DEG C 30 minutes modified under the state of recrystallized structure, when observing with EBSD after electrolytic polishing copper foil surface, the area occupation ratio being preferably the crystal grain of more than 15 degree from the differential seat angle of [100] orientation is less than 20%.The temperature experience of giving Copper Foil in CCL manufacturing step is imitated in the annealing of above-mentioned 200 DEG C 30 points.In addition, becoming the Copper Foil of CCL to receiving thermal history, also can heat 30 minutes at 200 DEG C.Heat treatment, until the tissue of Copper Foil of primary recrystallization, even if heat on this, also has almost no change again, when therefore observing with EBSD, the Copper Foil receiving thermal history and the Copper Foil do not accepted as broad as long, and all to heat 30 minutes at 200 DEG C.
When observing with EBSD, if above-mentioned area occupation ratio is less than 20%, then the misorientation that the crystal grain of copper foil surface is mutual is little, and the ratio that the crystal grain that crystal orientation is different in uniform tissue exists individually tails off, and therefore reduces by etching the depression (dish-like sagging) caused.In addition, when utilizing EBSD to observe, 20% is less than for making above-mentioned area occupation ratio, the growth of shear band can be suppressed in rolling pass as mentioned above in finally cold rolling before final rolling pass, in the rolling pass namely before finally cold rolling final rolling pass, use roughness (surface roughness Ra is such as less than 0.05 μm) smaller roller to be rolled.
(6) form
As Copper Foil, can use the tough pitch copper of more than purity 99.9wt%, oxygen-free copper, in addition, intensity as requested, electric conductivity can use known copper alloy.Oxygen-free copper specification is JIS-H3510(alloy numbering C1011), JIS-H3100(alloy numbering C1020), tough pitch copper specification is JIS-H3100(alloy numbering C1100).
As known copper alloy, such as, the copper alloy (being more preferably mixed with the copper alloy of 0.001 ~ 0.02wt% tin) being mixed with 0.01 ~ 0.3wt% tin can be enumerated; Be mixed with the copper alloy of 0.01 ~ 0.05wt% silver; Be mixed with the copper alloy of 0.005 ~ 0.02wt% indium; Be mixed with the copper alloy of 0.005 ~ 0.02wt% chromium; To amount to below 0.05wt% containing more than one the copper alloy etc. be selected from tin, silver, indium and chromium, wherein, as excellent electric conductivity person, use Cu-0.02wt%Ag more.
Then, an example of the manufacture method of rolled copper foil of the present invention is described.First, by copper and necessary alloying element 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 making the surface of Copper Foil too coarse before finally cold rolling final rolling pass, and make the surface of Copper Foil roughening in finally cold rolling final rolling pass, make the surface of final Copper Foil roughening thus, Shear heating instability tails off simultaneously, and flexibility improves, and dish-like sinking tails off.Further, the surface that this Shear heating instability is few becomes G60 rD/ G60 tD< 0.8.
Therefore, before finally cold rolling final rolling pass, in order to not make the surface of Copper Foil too coarse, 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 rolling pass degree of finish be rolled.On the other hand, use roughness (surface roughness Ra is such as more than 0.06 μm) larger roller to be rolled in finally cold rolling final rolling pass, or use the high ROLLING OIL of viscosity to be rolled, make the copper foil surface of final gained coarse.
In addition, in order to make the surface of final Copper Foil roughening, Shear heating instability tails off simultaneously, in finally cold rolling final 2 rolling passes or final rolling pass, as mentioned above, need to use coarse roller or use the high ROLLING OIL of viscosity to be rolled, but from the easy aspect of adjustment, the rolling condition preferably in the final rolling pass of adjustment.On the other hand, if by time roughening for the roughness of roller before finally cold rolling final 3 rolling passes, then Shear heating instability is grown up.
In addition, adjustable annealing conditions, with make finally cold rolling before the average grain diameter of recrystallization grain of annealing gained be 5 ~ 20 μm.In addition, can make finally cold rolling in rolling degree of finish be more than 90%.
Embodiment
Cast using the tough pitch copper that with the addition of the element formed shown in table 1 or oxygen-free copper as the ingot casting of raw material, 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, finally being refined to thickness in finally cold rolling is 0.012mm(embodiment 1 ~ 9, comparative example 1 ~ 7).Wherein, in embodiment 10, make fine finishining thickness be 0.018mm, in embodiment 11, make fine finishining thickness be 0.006mm.Make finally cold rolling in rolling degree of finish be 99.2%.
In addition, finally cold rollingly carry out 10 ~ 15 rolling passes, as shown in table 1, the surface roughness changing the surface roughness of the roller before final rolling pass and the roller of final rolling pass is rolled.The surface roughness of the roller before from the 1st rolling pass of final rolling pass to final rolling pass is identical.
In addition, " adding the TPC of 0.02%Ag " in the composition hurdle of table 1 points to JIS-H3100(alloy numbering C1100) tough pitch copper (TPC) in the addition of the Ag of 0.02 quality %.In addition, " adding the OFC of 0.007%Sn " in the composition hurdle of table 1 points to JIS-H3100(alloy numbering C1020) oxygen-free copper (OFC) in the addition of the Sn of 0.007 quality %.Wherein, in embodiment 6, only employ specification is JIS-H3510(alloy numbering C1011) oxygen-free copper (OFC) as oxygen-free copper, embodiment 4,5,7,9,10, to employ specification be JIS-H3100(alloy numbering C1020 to comparative example 7) oxygen-free copper (OFC) as oxygen-free copper.
To each Copper Foil sample obtained like this, carry out the evaluation of each characteristic.
(1) glossiness
Respectively along rolling parallel direction RD, and rolling vertical direction TD, the glossiness G60 of copper foil surface is measured according to JIS-Z8741 rD, G60 tD.
(2) cube set tissue
After sample is heated 30 minutes at 200 DEG C, obtain the integrated value (I) of (200) face intensity of being tried to achieve by the X-ray diffraction of rolling surface.By the integrated value (I0) of this value divided by (200) face intensity of the micro mist copper measured in advance (325 orders heat after 1 hour in the hydrogen gas stream and use at 300 DEG C), calculate I/I0 value.
(3) depth capacity (mean value d) in oil hole
Use contact roughmeter (little slope studies made SE-3400), as shown in Figure 3, obtaining respectively at copper foil surface in rolling parallel direction RD length is 175 μm, and 3 straight line L of more than 50 μm of being separated by respectively on the vertical direction TD of rolling 1~ L 3on maximum height H mwith minimum constructive height H sdifference di.By each straight line L 1~ L 3di be averaging and be designated as d.In addition, d (mm)/t (mm) is designated as.
(4) misorientation of EBSD is utilized
EBSD(backscattered electron ray diffraction device is used after heating the specimen surface electrolytic polishing after 30 minutes in (2) at 200 DEG C, Jeol Ltd. JXA8500F, accelerating potential 20kV, electric current 2e-8A, measurement range 1000 μm × 1000 μm, step-length 5 μm) observe.Being obtained from the differential seat angle of [100] orientation by image analysis is the area occupation ratio of the crystal grain of more than 15 degree.And then, the number being greater than 20 μm at the range of observation intercrystalline particle diameter that specimen surface 1mm is square with visual counting.And, to the sample comprising this range of observation, use ア デ カ テ ッ Network CL-8(Co., Ltd. ア デ カ system) 20% solution, etch 2 minutes at normal temperatures, with the surface after the etching of optics microscope photographing, by gained image light and shade binaryzation, the dark portion of minor axis more than 50 μm is counted as dish-like sinking.In addition, the copper foil surface after etching becomes the shape reflecting crystal orientation, and the tissue with [100] orientation becomes the face parallel with copper foil surface, in contrast, have other crystal orientation part occur because of crystal orientation cause concavo-convex.Therefore, dark by sagging part dish-like during observation by light microscope.
In addition, 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 1.In Fig. 6, Fig. 7, the region representation of grey, black is the crystal grain of more than 15 degree from the differential seat angle of [100] orientation.
(5) scar on surface
The surface of each sample of visualization, has the scar of more than 10mm length in rolling direction, 5 places/m 2above situation is designated as ×.
(6) flexibility
Sample heated 30 minutes at 200 DEG C and after recrystallization, utilizes the deflection test setup shown in Fig. 4, carrying out the mensuration of flex fatigue life.This device is structure oscillatory driver 4 combining vibration driving member 3, and the part of screw 2 represented by arrow by test Copper Foil 1 and the leading section of 3 are amounted at 4 and be fixed on device.When vibration section about 3 drives, the pars intermedia of Copper Foil 1 bends as U-shaped with the radius of curvature r of regulation.In this experiment, obtain under the following conditions when repeatedly bending until the number of times of fracture.
In addition, when thickness of slab is 0.012mm, experimental condition is as described below: test film width: 12.7mm, test film length: 200mm, direction taked by test film: become the mode parallel with rolling direction with the length direction of test film and take, radius of curvature r:2.5mm, vibrating stroke: 25mm, vibration velocity: 1500 beats/min.In addition, when flex fatigue life is more than 30,000 times, be judged as that there is excellent flexibility.
In addition, when thickness of slab is respectively 0.018mm, 0.006mm, bending test when being 0.012mm in order to make bending strain with thickness of slab is identical, and radius of curvature r is changed into 4mm, 1.3mm respectively, but other experimental conditions are identical.
The result obtained is shown in table 1.
[table 1]
As shown in Table 1, at G60 rDbe more than 100 and less than 300 and I/I 0>=50, and d/t is less than 0.1, G60 rD/ G60 tDwhen being less than each example of 0.8, what utilize EBSD is the crystal grain of more than 15 degree from the differential seat angle of [100] orientation area occupation ratio is less than 20%, and dish-like sagging number is few, and then does not have scar at copper foil surface, and flexibility is also excellent.
On the other hand, in finally cold rolling, until the surface roughness of the surface roughness of roller before final rolling pass and the roller of final rolling pass is the situation of the comparative example 1,5,7 of less than Ra=0.05 μm, the G60 of copper foil surface rDmore than 300, copper foil surface is with scar, and operability is poor.In addition, in the situation of comparative example 5, the rolling degree of finish step-down in finally cold rolling is 96%, therefore I/I 0< 50, even if glossiness improves, from the differential seat angle of [100] orientation be the area occupation ratio of the crystal grain of more than 15 degree also more than 20%, dish-like sinking can be produced in a large number.
In finally cold rolling, until the surface roughness of roller before final rolling pass roughening be more than Ra=0.06 μm, when the surface roughness of the roller of final rolling pass is less than Ra=0.05 μm comparative example 2, above-mentioned area occupation ratio is more than 20%, and dish-like sagging number increases.In addition, the G60 of copper foil surface rDmore than 300, at copper foil surface with scar, operability is poor.
In finally cold rolling, until the surface roughness of the surface roughness of roller before final rolling pass and the roller of final rolling pass all roughening be the comparative example 3,4 of more than Ra=0.06 μm, when 6, above-mentioned area occupation ratio is more than 20%, and dish-like sagging number increases.
In addition, at comparative example 3, when 4, the roll surface roughness of finally cold rolling all rolling passes becomes coarse, and therefore Shear heating instability is grown up at material internal, and the degree of orientation of the crystallization of copper foil surface reduces, and becomes I/I 0< 50.On the other hand, when comparative example 6, until the roughness of roller before final rolling pass comparatively comparative example 3,4 is level and smooth, therefore glossiness and I/I 0become the value all high compared with comparative example 3,4, but the suppression of shear band becomes insufficient, above-mentioned area occupation ratio is more than 20%, and dish-like sagging number increases.In addition, can think until roller roughness before final rolling pass be 0.07 μm state under, have and plate speed reduced with the method suppressing shear band etc., but now glossiness more than 300, injurious surface mark is judged to be ×.

Claims (3)

1. rolled copper foil, wherein, measures 60 degree of glossiness G60 according to JIS-Z8741 on the surface obtained in rolling parallel direction rDbe more than 100 and less than 300, under 200 DEG C of heating, 30 minutes modified states 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,
Copper foil surface in rolling parallel direction length be 175 μm, and be separated by 3 straight lines of more than 50 μm respectively in rolling vertical direction, the mean value d of the maximum height of the thickness direction of each straight line and the difference of minimum constructive height, and the ratio d/t of the thickness t of aforementioned Copper Foil is less than 0.1
60 degree of glossiness G60 according to JIS-Z8741 on the surface obtained are measured in rolling parallel direction rD, and the 60 degree of glossiness G60 according to JIS-Z8741 on the surface that rolling vertical direction measures tDratio G60 rD/ G60 tDbe less than 0.8.
2. rolled copper foil according to claim 1, wherein, after the copper foil surface electrolytic polishing after heat treatment in described 200 DEG C × 30 minutes, when utilizing backscattered electron ray diffraction device to observe, the area occupation ratio being the crystal grain of more than 15 degree from the differential seat angle of [100] orientation is less than 20%.
3. rolled copper foil according to claim 1 and 2, wherein, after ingot bar hot rolling, cold rolling and annealing repeatedly, finally carry out finally cold rolling and manufacture, in this final cold rolling step, in the stage of the last rolling pass of final rolling pass, at 60 degree of glossiness G60 on the surface that rolling parallel direction measures rDbe greater than 300.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237489A (en) * 1998-03-31 1999-12-08 日矿金属株式会社 Rolled copper foil and method of manufacturing the same
CN101293256A (en) * 2007-04-27 2008-10-29 来庆德 Rolling technique for silver staining narrow copper foil belt

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JP2001058203A (en) * 1999-08-19 2001-03-06 Nippon Mining & Metals Co Ltd Rolled copper foil excellent in bendability
JP4522972B2 (en) * 2005-04-28 2010-08-11 日鉱金属株式会社 High gloss rolled copper foil for copper-clad laminates
JP4354930B2 (en) 2005-04-28 2009-10-28 日鉱金属株式会社 Low gloss rolled copper foil for copper-clad laminates
JP2007268596A (en) * 2006-03-31 2007-10-18 Nikko Kinzoku Kk Copper alloy foil for roughening treatment
JP2009292090A (en) * 2008-06-06 2009-12-17 Nippon Mining & Metals Co Ltd Two-layer flexible copper-clad laminated sheet excellent in flexibility and method for manufacturing it
KR101269708B1 (en) * 2008-12-26 2013-05-30 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 Rolled copper foil or electrolytic copper foil for electronic circuit, method for forming electronic circuit and printed substrate using the rolled copper foil or electrolytic copper foil

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237489A (en) * 1998-03-31 1999-12-08 日矿金属株式会社 Rolled copper foil and method of manufacturing the same
CN101293256A (en) * 2007-04-27 2008-10-29 来庆德 Rolling technique for silver staining narrow copper foil belt

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