CN103361509B - Rolled copper foil, copper-clad laminated board, flexible printing wiring board and manufacture method thereof - Google Patents
Rolled copper foil, copper-clad laminated board, flexible printing wiring board and manufacture method thereof Download PDFInfo
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- CN103361509B CN103361509B CN201310122528.1A CN201310122528A CN103361509B CN 103361509 B CN103361509 B CN 103361509B CN 201310122528 A CN201310122528 A CN 201310122528A CN 103361509 B CN103361509 B CN 103361509B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 239000011889 copper foil Substances 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000007639 printing Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005452 bending Methods 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims description 65
- 239000010949 copper Substances 0.000 claims description 65
- 238000000137 annealing Methods 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 28
- 238000005096 rolling process Methods 0.000 claims description 28
- 238000005097 cold rolling Methods 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 238000005098 hot rolling Methods 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 7
- 230000000116 mitigating effect Effects 0.000 abstract description 11
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 229920001721 polyimide Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002040 relaxant effect Effects 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001887 electron backscatter diffraction Methods 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- 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
- H05K1/03—Use of materials for the substrate
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Non-Insulated Conductors (AREA)
- Conductive Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to rolled copper foil, copper-clad laminated board, flexible printing wiring board and manufacture method thereof.Its problem is to provide a kind of for bending rolled copper foil, copper-clad laminated board, the flexible printing wiring board (FPC) with the weather resistance more spent.Its solution is that a kind of interval decreasing the mitigation of the stress in bending bends tolerance Copper Foil.
Description
Technical field
The present invention relates to rolled copper foil, copper-clad laminated board, flexible printing wiring board and manufacture method thereof.
Background technology
Electronics is formed with multiple electric substrate usually, is arranged between electric substrate the flexible printing wiring board (being sometimes recited as FPC below) that these electric substrates are electrically connected each other.The copper wiring that flexible printing wiring board usually possesses insulated substrate and formed at this substrate surface.For connection electric substrate flexible printing wiring board each other, require good bendability etc.
Particularly in recent years, because the miniaturized electronics possessing the portable phone, digital camera, pick up camera etc. of the movable part that folded part, rotating part or slip pulling unit grade is popularized, continuous miniaturization, slimming, densification, so become higher to the bendability that the flexible printing wiring board used in moving part requires.
As the characteristic required such flexible printing wiring board, have with MIT bendability that to be representative good is flexibility, and with the high reversed bending that IPC bendability is representative, in the past, develop the Copper Foil, the copper-resin substrate duplexer (patent documentation 1 ~ 2) that possess such characteristic.
Such as, in slip pliability test (IPC), use-testing device can tolerate the number of bends of more than 100,000 times such, the flexible printing wiring board goods that can tolerate the number of bends that generally can not have in reality.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-100887 publication;
Patent documentation 2: Japanese Unexamined Patent Publication 2009-111203 publication.
The problem that invention will solve
; even be used in slip pliability test (IPC) miniaturized electronics, such as folder-type portable telephone, the sliding-type portable phone of the flexible printing wiring board that can tolerate the number of bends (such as 100,000 times) that generally can not have in reality; in the goods of reality, the fault of flexible printing wiring board fracture does not disappear.Even if as the reason using the FPC that can tolerate huge number of bends but still to produce such fault in the goods of reality, discussed the contact of the parts that densification causes, reason that the deterioration of insulating material that be full of cracks that the top of miscellaneous part to the sandwiching of FPC, sharp component causes, the heating outside design, chemical reaction cause etc. is countless, and be applied with countermeasure.
Present inventor does not have situation about disappearing in view of the fault of flexible printing wiring board fracture in the goods of reality, considers the reason of not seeking these faults in addition, and can solve this problem by the Copper Foil of improvement FPC itself, and research and develop.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of when using in FPC in the goods of reality, for bending rolled copper foil, copper-clad laminated board, the flexible printing wiring board (FPC) with higher weather resistance.
For solving the scheme of problem
In such a case, present inventor considers the situation that the fault ruptured in fact still occurs the flexible printing wiring board that can tolerate the number of bends (such as 100,000 times) that generally can not have in reality in slip pliability test (IPC) in the goods (such as folder-type portable telephone, sliding-type portable phone) of reality, think even so, by the further improvement of FPC, or these can be avoided to rupture, and carried out studying with keen determination.
And, present inventor conceives the environment for use that the present slip pliability test (IPC) having become the test method of standard does not have slice-of-life goods, and reduce the number of bends (time per unit) in pliability test on the contrary and carried out various experimental investigation, shockingly find by giving off and on bending, thus easily produced the phenomenon of fracture.
On this basis, present inventor found this phenomenon beyong contemplation due to Copper Foil stress relax phenomenon produce, exactly because found the Copper Foil pursuing the FPC of slimming, cause it is generally acknowledged that the stress only with theoretic possibility relaxes the fracture of phenomenon on the goods of reality and causes large impact, find in the manufacture of Copper Foil, relax by not making stress as far as possible and produce, thus bending tolerance is significantly improved under the condition that the goods of reality are run into, thus achieve the present invention.
Namely, according to the present invention, by coming manufacturing copper foil and FPC to meet the mode making the stress of the Copper Foil of FPC relax the condition reduced, thus the bending weather resistance to interval can be improved, the fracture of the FPC under the condition that the goods that can reduce reality run into.Therefore, reduce stress and relax, the FPC that the bending tolerance of interval is improved and Copper Foil also do not rely on the means that its concrete minimizing stress relaxes, within the scope of the present invention.
Therefore, the invention reside in following (1) ~.
（1）
The bending tolerance Copper Foil of a kind of interval, the stress decreased in bending relaxes.
（2）
A kind of interval described in (1) bends tolerance Copper Foil, relative in 25 DEG C 0.2% distortion, meet the condition of formula I below:
(T
0-T
5)/T
0≤ 25(%) (formula I)
(wherein, T
0represent initial stress, T
5represent the stress after 5 hours).
（3）
The bending tolerance Copper Foil of a kind of interval, observes from rolling parallel sections, often observes sectional area 1000 μm
2the length of crystal grain boundary be less than 200 μm.
（4）
Interval according to (1) or (2) bends tolerance Copper Foil, observes from rolling parallel sections, often observes sectional area 1000 μm
2the length of crystal grain boundary be less than 200 μm.
（5）
Interval according to any one of (1) ~ (4) bends tolerance Copper Foil, has the Young's modulus of the scope of 60 ~ 105GPa.
（6）
Interval according to any one of (1) ~ (5) bends tolerance Copper Foil, and Copper Foil is containing copper and the Copper Foil that can not keep away impurity and be formed.
（7）
Interval according to any one of (1) ~ (5) bends tolerance Copper Foil, and Copper Foil is containing copper and can not keep away impurity, also to add up to 20 ~ 500 quality ppm to contain the Copper Foil formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed.
（8）
Interval according to any one of (1) ~ (5) bends tolerance Copper Foil, and Copper Foil is the Copper Foil be made up of oxygen free copper or tough pitch copper.
（9）
Interval according to any one of (1) ~ (5) bends tolerance Copper Foil, and Copper Foil is also to add up to 20 ~ 500 quality ppm to be added with the Copper Foil formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed outside oxygen free copper or tough pitch copper.
（10）
Interval according to any one of (1) ~ (9) bends tolerance Copper Foil, and Copper Foil is rolled copper foil.
（11）
Interval according to any one of (1) ~ (10) bends tolerance Copper Foil, and Copper Foil is with the rolled rolled copper foil of degree of finish more than 96%.
（12）
Interval according to any one of (1) ~ (11) bends tolerance Copper Foil, and Copper Foil is the Copper Foil of flexible printing wiring board.
（13）
Interval according to any one of (1) ~ (11) bends tolerance Copper Foil, and copper foil layer is stacked in flexible printing wiring board.
（14）
Interval according to any one of (1) ~ (11) bends tolerance Copper Foil, and Copper Foil is the Copper Foil of copper-clad laminated board.
（15）
Interval according to any one of (1) ~ (11) bends tolerance Copper Foil, and copper foil layer is stacked in copper-clad laminated board.
And then, the invention reside in following (21) ~.
（21）
A kind of Copper Foil, carry out with 160 ~ 400 DEG C 1 second ~ heat treated of 1 hour after, to become (1) ~ interval described in any one of (14) bends tolerance Copper Foil.
（22）
A kind of Copper Foil, carrying out the heat treated of 30 minutes with 200 DEG C, or after carrying out the heat treated in 1 second with 350 DEG C, becoming (1) ~ interval described in any one of (14) bends tolerance Copper Foil.
（23）
A kind of flexible printing wiring board, be laminated with (1) ~ (10), (11), (12) the interval described in any one bend tolerance Copper Foil and form.
（24）
A kind of copper-clad laminated board, be laminated with (1) ~ (10), (13), (14) the interval described in any one bend tolerance Copper Foil and form.
And then, the invention reside in following (31) ~.
（31）
A manufacture method for rolled copper foil, comprises:
The operation of the ingot casting of casting copper;
The ingot casting of copper is carried out to the operation of hot rolling;
The ingot casting of the copper to hot rolling carries out the operation of the cold rolling and annealing of more than 1 time; And
Carry out the last cold rolling operation for making finished product thickness.
（32）
Manufacture method according to (31), is carrying out for making in the last cold rolling operation of finished product thickness,
Being used in the last cold rolling total degree of finish (final rolling degree of finish) making finished product thickness is more than 96%.
（33）
Manufacture method according to any one of (31) ~ (32), carries out in the operation of cold rolling and annealing of more than 1 time at the ingot casting of the copper to hot rolling,
The annealing finally carried out is carried out with the heat-up rate of more than 5 DEG C/sec less than 40 DEG C/sec.
（34）
Manufacture method according to any one of (31) ~ (33), carries out in the operation of cold rolling and annealing of more than 1 time at the ingot casting of the copper to hot rolling,
The cold rolling degree of finish (total degree of finish) with 60% ~ 90% carried out slightly before of the annealing finally carried out carries out.
（35）
Manufacture method according to any one of (31) ~ (34), the ingot casting of copper is containing copper and the ingot casting of copper that can not keep away impurity and be formed.
（36）
Manufacture method according to any one of (31) ~ (35), the ingot casting of copper is containing copper and can not keeps away impurity, also with the ingot casting adding up to 20 ~ 500 quality ppm to contain the copper formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed.
（37）
Manufacture method according to any one of (31) ~ (34), the ingot casting of copper is the ingot casting of the copper be made up of oxygen free copper or tough pitch copper.
（38）
Manufacture method according to any one of (31) ~ (34), (37), the ingot casting of copper is also with the ingot casting adding up to 20 ~ 500 quality ppm to be added with the copper formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed outside oxygen free copper or tough pitch copper.
And then, the invention reside in following (41) ~.
（41）
Interval bends a manufacture method for tolerance Copper Foil, comprises: the rolled copper foil that the manufacture method by any one of (31) ~ (36) is manufactured with 160 ~ 400 DEG C carry out 1 second ~ operation of heat treated of 1 hour.
（42）
Interval bends a manufacture method for tolerance flexible printing wiring board, comprises:
The rolled copper foil that will be manufactured by the manufacture method of any one of (31) ~ (36) and the stacked operation of matrix resin; And
To with the stacked rolled copper foil of matrix resin with 160 ~ 400 DEG C carry out 1 second ~ operation of heat treated of 1 hour.
（43）
A manufacture method for copper-clad laminated board, comprises:
The rolled copper foil that will be manufactured by the manufacture method of any one of (31) ~ (36) and the stacked operation of matrix resin; And
To with the stacked rolled copper foil of matrix resin with 160 ~ 400 DEG C carry out 1 second ~ operation of heat treated of 1 hour.
And then, the invention reside in following (51) ~.
（51）
A kind of rolled copper foil, by the manufacture method manufacture of any one of (31) ~ (36).
（52）
The bending tolerance Copper Foil of a kind of interval, by the manufacture method manufacture of (41).
（53）
The bending tolerance flexible printing wiring board of a kind of interval, by the manufacture method manufacture of (42).
（54）
A kind of copper-clad laminated board, by the manufacture method manufacture of (43).
The effect of invention
According to the present invention, the bending tolerance Copper Foil of interval can being obtained, obtaining when using in FPC in the goods of reality, for bending rolled copper foil, copper-clad laminated board, the flexible printing wiring board (FPC) with higher weather resistance.Possessing interval of the present invention in use bends in the electronics of flexible printing wiring board (FPC) of tolerance Copper Foil, because the FPC becoming its movable part possesses the bending tolerance of the behaviour in service in the goods reflecting reality, so compared with the existing goods only considered the tolerance that continuous print bends, weather resistance, of superior reliability.
Accompanying drawing explanation
Fig. 1 is the explanatory view representing the bending internal surface of Copper Foil and the state of outside surface.
Fig. 2 is the explanatory view of the skew that Narrow Hystersis is described.
Fig. 3 is the electron micrograph of the rolling parallel sections for observing crystal grain boundary.
Embodiment
Below, enumerate preferred embodiment, explain the present invention.
As mentioned above, in the past, utilize continuous print bending motion to carry out the bendability evaluation of Copper Foil., present inventor finds, compared with bending, exists at the bending middle of interval with the situation of less number of bends Copper Foil with regard to fracture with continuous print.And, find that the change of this rupture life results from the stress of Copper Foil and relaxes phenomenon, thus reach the present invention.
According to the investigation of present inventor, when making Copper Foil alternating bending, at copper foil surface, tensile stress and stress under compression alternately work.If continuous print bends, no matter repeatedly bend several times, the stretching/compressing stress worked also is same degree.The pliability test of carrying out in this condition is the pliability test of in the past carrying out., when interval bending, produce stress between bending and bending and relax, Narrow Hystersis (hysteresis loop) is to the skew of low-stress side, and therefore when starting bending again, Narrow Hystersis is from original skew, and result stress amplitude becomes greatly.Present inventor has shown that this causes the bending ratio continuous print of interval to bend the conclusion becoming life-span short reason.
The explanatory view of this phenomenon is described shown in Fig. 1.Fig. 1 represents the bending inner side and outer side at imagination Copper Foil, when being divided into outside surface (outside surface) and internal surface (inner surface), and the explanatory view that outside surface becomes stretched state, internal surface becomes compressed state.As illustrated, because outer surface is in stretched state, if so maintain this state, then can produce stress under this stretched state soon and relax, result, become about outside surface the state that Narrow Hystersis offsets to compressed side.On the other hand, as illustrated, because internal surface is in compressed state, if so maintain this state, then can produce stress under this compressed state soon and relax, result, become about internal surface the state that Narrow Hystersis offsets to tensile side.
Fig. 2 illustrates the explanatory view of the skew that such Narrow Hystersis is described.The transverse axis of Fig. 2 represents distortion, and the longitudinal axis represents stress.In fig. 2,3 Narrow Hystersiss of top, central part, bottom are shown.The Narrow Hystersis of central part is the Narrow Hystersis when bending continuously.If do not produce stress to relax the skew caused, then Narrow Hystersis was positioned at the position of the Narrow Hystersis as this central part originally.In the continuous print pliability test of in the past carrying out, the pliability test of such as to carry out 100,000 times along this Narrow Hystersis can be said.Therefore, if the use of FBC in the miniaturized electronics of reality is carried out along such Narrow Hystersis, FBC all should tolerate bending such as more than 100,000 times, and such endurance quality that each manufacturer expects is shown.
The Narrow Hystersis on the top of Fig. 2 be Copper Foil is bent and with the time observe after producing stress and relaxing, the inner surface side of the Copper Foil Narrow Hystersis because stress relaxes after skew.The Narrow Hystersis of the bottom of Fig. 2 be Copper Foil is bent and with the time observe after producing stress and relaxing, the outside surface side of the Copper Foil Narrow Hystersis because stress relaxes after skew.Like this, bend making Copper Foil and keep, producing stress along with the process of time when relaxing, same Copper Foil, outside surface side and inner surface side, there is different Narrow Hystersiss like this.
And then after this, make Copper Foil bending to opposition side, namely, outside before making it becomes inner side specifically, make it before inner side become the mode in outside specifically when carrying out bending, from the Narrow Hystersis of the Narrow Hystersis lower portion on the top of Fig. 2, simultaneously from the Narrow Hystersis of bottom to the Narrow Hystersis on top, the two sides of Copper Foil is applied above to the large amplitude of each Narrow Hystersis.And then afterwards, if again make Copper Foil bend to opposition side and keep, then again the two sides of Copper Foil is applied above to the large amplitude of each Narrow Hystersis, result, if continue like this to carry out the bending of interval, then alternately produce stress on two sides and relax, stress, strain amplitude increase.The arrow of Fig. 2 represents the situation of the skew (amplitude) producing such Narrow Hystersis.When continuing to carry out interval bending like this, circulate with only making the Narrow Hystersis of central part and carry out compared with the bending situation of continuous print like that, harsh distortion is applied to Copper Foil, result, when not reaching if Copper Foil is just damaged continuous print bends the number of bends that just can tolerate.
Therefore, in order to avoid such breakage, present inventor contemplates the idea of the stress relaxation properties improving Copper Foil.Therefore, the invention reside in, relax by reducing stress, or prevent stress from relaxing generation, thus the bendability of the interval of Copper Foil is improved, and then be the Copper Foil (comprising the Copper Foil in FPC) that the bendability of interval thus improves.In this manual, the concrete embodiment that the bendability enumerating the interval for making Copper Foil improves comes that the present invention will be described, but the present invention not limit by the concrete embodiment enumerated like this.
And then in order to avoid such breakage, present inventor contemplates the Young's modulus by reducing Copper Foil thus can reduce the idea of the STRESS VARIATION relative to deflection.Thus, if even if when there occurs stress and relaxing, the increase of stress, strain amplitude also can be suppressed.Therefore, the present invention is also, by reducing the Young's modulus of Copper Foil thus improving the bendability of interval of Copper Foil, and then is the Copper Foil (comprising the Copper Foil in FPC) of the bendability by which raises interval.About this point, in this manual, the concrete embodiment that the bendability enumerating the interval for making Copper Foil improves comes that the present invention will be described, but the present invention not limit by the concrete embodiment enumerated like this.
[stress mitigation]
It is under the condition of fixing temperature, fixing distortion that stress relaxes, in the phenomenon that the stress of metal load reduced along with the time.
It is the phenomenon produced by the movement of the dislocation in material that stress relaxes on microcosmic.The movement of such dislocation easily produces in crystal grain boundary.Therefore, the present invention makes the minimizing of the length of the crystal grain boundary of Copper Foil be used as realizing the means that stress relaxes minimizing, thus achieves the raising of the bending tolerance relative to interval.
[crystal boundary length]
The length (crystal boundary length) of crystal grain boundary such as can be asked for as follows, namely, CP(Cross section polisher is used to carrying out the Copper Foil after annealing in 30 minutes with 200 DEG C, section polishing) and form rolling parallel sections, use EBSD(Electron Back Scattering Diffraction, EBSD, Jeol Ltd. JXA8500F), with step-length 0.5 μm, acceleration voltage 15kV, WD23mm, electric current 5 × 10
-8a is to range of observation 1000 μm
2crystalline orientation measure, the situation being more than 15 degree by the crystalline orientation difference with adjacent measuring point regards crystal grain boundary as, is determined at the crystal grain boundary length comprised in range of observation.
In a preferred embodiment, from the often observation sectional area 1000 μm that rolling parallel sections is seen
2the length of crystal grain boundary such as can be set to less than 200 μm, be preferably set to less than 100 μm, be preferably set to less than 90 μm further, be more preferably set to less than 70 μm, be further preferably set to less than 50 μm.Relax from the view point of minimizing stress, the length of crystal grain boundary is the smaller the better.On the other hand, in a preferred embodiment, the length of crystal grain boundary can be set to such as more than 0.1 μm, such as more than 1.0 μm, such as more than 5.0 μm.From the view point of the intensity of Copper Foil, the length of preferred crystal grain boundary is the value of more than this value.
In order to represent the length of crystal grain boundary, Fig. 3 illustrates an example of the electron micrograph of the rolling parallel sections observed.In figure 3,3 cross sectional photograph of upper, middle and lower are shown as the photo of growing crosswise.In the cross sectional photograph on the top of Fig. 3, almost can't see crystal grain boundary.This sample strip that almost can't see crystal grain boundary shows good interval and bends tolerance (good).Further, due to Copper Foil extremely thin, so supporting mass is connected to Copper Foil observes to obtain electron micrograph, the black part of the topmost of the cross sectional photograph on top is the gap of this supporting mass and Copper Foil, its just under white part be supporting mass.In the cross sectional photograph of the below of Fig. 3, observe many crystal grain boundaries.This sample strip being observed many crystal grain boundaries is the sample (bad) of the bending tolerance difference of interval.In the cross sectional photograph at the middle part of Fig. 3, observe moderate crystal grain boundary.This sample strip is more outstanding than the sample of the cross sectional photograph of above-mentioned bottom in the bending tolerance of interval, but poorer than the sample of the cross sectional photograph on above-mentioned top.
[stress mitigation rate]
Stress mitigation rate is asked for as follows, namely, the Copper Foil such as will carried out after annealing in 30 minutes with 200 DEG C, precision cutting tool is used to cut out the strip of width 12.7mm, use tensile testing machine (Shimadzu Scisakusho Ltd AGS-X), be fixed with chuck spacing 50mm, chuck spacing be stretched to 50.1mm and measure in the change of 25 DEG C of counter stresses, by the stress T obtained after t hour
twith the stress T of initial (after 0 hour)
0difference divided by initial stress T
0after value { (T
0-T
t)/T
0as the stress mitigation rate (%) after t hour.
In a preferred embodiment, interval of the present invention bends the stress mitigation rate (%) of tolerance Copper Foil when establishing t=5 hour, relative to being the distortion of 0.2% at 25 DEG C, can meet the condition of following formula I:
(T
0-T
5)/T
0≤ 25(%) (formula I)
(wherein, T
0represent initial stress, T
5represent the stress after 5 hours),
And then preferably can meet the condition of Formula Il:
(T
0-T
5)/T
0≤ 20(%) (formula II)
Condition.More preferably can by (T
0-T
5)/T
0value be set to less than 19%.
[Young's modulus]
Young's modulus such as can use resonant mode tester (Japanese technoplas Co., Ltd. TE-RT) to measure.Of the present invention preferred embodiment in, the Young's modulus of the bending tolerance Copper Foil of interval such as can be set to 60 ~ 105GPa, is preferably set to 70 ~ 105GPa, is preferably set to 70 ~ 100GPa further, more preferably be set to 70 ~ 90GPa, be further preferably set to the scope of 75 ~ 85GPa.
[component]
As long as the component that the component of Copper Foil of the present invention can reduce stress mitigation just can use.Such as, the fine copper comprising copper and impurity can not be kept away can be used.In a preferred embodiment, as the component of Copper Foil, can using the tough pitch copper meeting the specification of the alloy number C1100 of JIS-H3100 or the oxygen free copper of specification of alloy number C1020 meeting JIS-H3100 as component.When adopting such component close to fine copper, the electric conductivity of Copper Foil can not reduce, and is suitable for FPC, COF.Usually, the oxygen concn comprised in rolled copper foil is 0.01 ~ 0.05 quality % when tough pitch copper, is below 0.001 quality % when oxygen free copper.In addition, the oxygen free copper of the specification of the alloy number C1011 meeting JIS-H3510 can be used as oxygen free copper.
In a preferred embodiment, as the component of Copper Foil, also can to the above-mentioned component close to fine copper further to add up to below 500 quality ppm containing more than a kind that selects from the group of Ag and Sn.Wherein, the amount of preferred Sn is below 300ppm.When Ag or Sn to the total addition of rolled copper foil more than 500 quality ppm time, electric conductivity reduces and recrystallization temperature rises, and has the growth of recrystal grain in final annealing suppressed, the situation of crystal boundary length.Although the lower limit of the total addition of Ag and Sn does not have special stipulation, normally add up to more than 20 quality ppm.
In a preferred embodiment, in the copper of the above-mentioned component close to fine copper, such as in above-mentioned tough pitch copper or above-mentioned oxygen free copper, the element containing more than a kind that selects from the group of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V to add up to 20 ~ 500 quality ppm also can.
Have again, also the element of more than a kind can selected from the group of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V to add up to more than 500 quality ppm to be added with the copper of the above-mentioned component close to fine copper, such as apply the thermal treatment of more than 30 minutes by the high temperature more than 600 DEG C thus recrystal grain is grown, also can improve stress relaxation properties., in this operation, in order to manufacture copper-clad laminated board and must by not favourable in the soft Copper Foil after recrystallize and laminated resin.
[manufacture of Copper Foil]
The manufacture of Copper Foil of the present invention (the bending tolerance Copper Foil of interval) as described above, as long as can manufacture the method decreasing the Copper Foil that stress relaxes, then can be not particularly limited and carry out.In a preferred embodiment, by comprising the operation using copper (copper alloy) ingot casting to copper of said components to cast, the operation of the ingot casting of copper being carried out to hot rolling, to carry out the ingot casting of the copper after hot rolling more than 1 time cold rolling and the operation of annealing, the manufacture method of last cold rolling operation of carrying out for making finished product thickness manufacture rolled copper foil, by this rolled copper foil is carried out with 160 ~ 400 DEG C carry out 1 second ~ operation of 1 hour heat treated, thus the bending tolerance Copper Foil of interval can be manufactured.In addition, above-mentioned with 160 ~ 400 DEG C carry out 1 second ~ heat treated of 1 hour, also can double as the thermal treatment in the manufacturing process of the copper-clad laminated board for making Copper Foil engage with resin layer.
In the operation of cold rolling and annealing of the ingot casting of the copper after this hot rolling being carried out to more than 1 time, repeatedly can carry out cold rolling and annealing aptly, make desired thickness.In a preferred embodiment, in the annealing preferably finally carried out in this annealing, the annealing namely carried out slightly before in the last cold rolling operation of carrying out for making finished product thickness, heat-up rate is set to more than 5 DEG C/sec less than 40 DEG C/sec.When heat-up rate is below 5 DEG C/sec, the coarsening of crystal grain occurs, and recrystallized structure becomes uneven.On the other hand more than 40 DEG C/sec, because fine recrystal grain grows respectively, so recrystallized structure becomes uneven.
In a preferred embodiment, in the rolling that the above-mentioned annealing finally carried out is carried out slightly before, degree of finish (total degree of finish) such as can be set to less than 90%, preferably be set to less than 89%, more preferably less than 88% is set to, such as can be set to more than 60%, preferably be set to more than 65%, more preferably be set to more than 67%.By adopting such scope, uniform recrystallized structure can be realized after this annealing operation, suitable rolling structure can be made in final rolling process.When total degree of finish of the rolling process carried out slightly before of the annealing in the end carried out is more than 90%, set excessive tissue is flourishing, the easy coarsening of the crystal grain after annealing operation.
In a preferred embodiment, carrying out for making in the last cold rolling operation of finished product thickness, this last cold rolling total degree of finish (final rolling degree of finish) can be set to more than 96%, preferably be set to more than 97%, be more preferably set to more than 97.5%.
Further, those skilled in the art understand, in each rolling process of the present invention, a rolling process also can make material Multiple through then out (repeatedly passing through) Rolling roller implement.Therefore, in present specification, the degree of finish of certain rolling process, mean when by so be repeatedly rolled operation through coming, the degree of finish of implementation trade-off by repeatedly passing through, not being the degree of finish (1 time through degree of finish) of the process of arbitrary time that comprises in this rolling process, in order to make it definitely, sometimes the degree of finish of certain rolling process being recited as total degree of finish.
In a preferred embodiment, rolled copper foil is carried out with 160 ~ 400 DEG C 1 second ~ 1 hour heat treated operation in, such as can with 200 ~ 400 DEG C carry out 1 second ~ heat treated of 30 minutes, such as can carry out the heat treated of 30 minutes with 200 DEG C, such as, can carry out the heat treated in 1 second with 350 DEG C.Further, heat-up time also can be shorter than 1 second, such as 0.1 second ~ 1 second.By this heat treated, be above-mentionedly subject to last cold rolling rolled copper foil and become stress and relax the interval of the present invention decreased and bend tolerance Copper Foil.This heat treated carries out also can as to the independently operation of rolled copper foil, but such as in order to manufacture copper-clad laminated board and stacked resin, when thermo-compressed is carried out to membranaceous resin, carry out heat treated in the mode becoming this heat treated condition also can, or such as in order to manufacture copper-clad laminated board and stacked resin, when coated with resins material makes its thermofixation and forms rete, carry out heat treated in the mode becoming this heat treated condition and also can.
[flexible printing wiring board]
Copper Foil of the present invention (the bending tolerance Copper Foil of interval) has superior interval as described above and bends tolerance, can use aptly as the wiring portion of the electroconductibility of flexible printing wiring board.Therefore, the present invention is also stacked and possesses the flexible printing wiring board of above-mentioned Copper Foil.
Flexible printing wiring board is formed by the wiring laminated resin in insulativity of electroconductibility usually, is flexibility and has bendability.Wiring is laminated in the resin layer of the base material of insulativity as required via adhesive linkage.All illustrate that outstanding interval bends tolerance in the mode that Copper Foil of the present invention any layers in office is folded, as long as therefore flexible printing wiring board of the present invention is stacked and possess the flexible printing wiring board of Copper Foil of the present invention, various concrete mode just can be adopted.In a preferred embodiment, be such as be bonded with Copper Foil of the present invention at membranaceous resin layer flexible printing wiring board also can, be at Copper Foil coated with resins material of the present invention film forming to be membranaceous flexible printing wiring board also can.For resin layer, be not particularly limited and the resin that can use in flexible printing wiring board can be used.In a preferred embodiment, such as polyimide resin can be used.
Flexible printing wiring board of the present invention such as can manufacture as follows.Apply the polyimide precursor of polyamic acid as main body at the one side of rolled copper foil, carry out drying and solidification, be processed into the copper-clad laminated board of polyimide resin layer and copper foil layer, the circuit of regulation is formed by photoetching, and then the bonding polyimide film in face in the wiring side of copper foil layer, can flexible printing wiring board be made.In above-mentioned copper-clad laminated board, as long as the layer of Copper Foil is interval bend tolerance Copper Foil, therefore, as the rolling Copper Foil, use the heat treated by the formation for polyimide resin layer, such as, be subject to the heat treated of 200 DEG C 30 minutes and become the Copper Foil that interval of the present invention bends tolerance Copper Foil.In addition, such as, at the bonding polyimide film of the one side of rolled copper foil, be processed into the copper-clad laminated board of polyimide resin layer and copper foil layer, the operation that the photoetching after carrying out is later, make flexible printing wiring board and also can.In this case, in above-mentioned copper-clad laminated board, as long as the layer of Copper Foil is interval bend tolerance Copper Foil, therefore, use as the rolling Copper Foil, by the bonding heat treated for polyimide film, such as, be subject to the heat treated of 200 DEG C 30 minutes and become the Copper Foil that interval of the present invention bends tolerance Copper Foil.
Interval of the present invention bends tolerance Copper Foil and uses its flexible printing wiring board can use aptly in the industrial machinery of the movable part, machine for automatic working, robots arm etc. of the electronics of the Wiring member, HDD etc. in the lens barrel portion of portable phone, notebook computer, photographic camera.
[embodiment]
Below, together examples and comparative examples of the present invention are shown, these embodiments, in order to understand the present invention and advantage thereof better and provide, do not limit the present invention.
[manufacture of Copper Foil]
Dissolve oxygen free copper (JIS alloy number C1020) (OFC:Oxygen-Free Copper) or tough pitch copper (JIS alloy number C1100) (TPC:Tough-Pitch Copper), element shown in interpolation table 1 is cast as required, makes the ingot casting of thickness 200mm, width 600mm.After by slab hot-rolling to thickness 10mm, repeatedly carry out cold rolling and annealing, be used in the last cold rolling degree of finish (final rolling degree of finish) making finished product thickness and be respectively the such of table 1 record, manufactured rolled copper foil.At this moment final rolling degree of finish and paper tinsel thick be respectively in table 1 record such.
In addition, the heat-up rate in total degree of finish and final cold rolling annealing operation slightly before of the rolling process carried out slightly before of final cold rolling annealing operation is slightly before as shown in table 1.Further, the "○" of heat-up rate means that heat-up rate is more than 5 DEG C/sec less than 40 DEG C/sec.In addition, the heat-up rate that the "×" of comparative example 7 means more than 40 DEG C/sec is annealed.
[evaluation]
After the annealing of 30 minutes is carried out with 200 DEG C to the rolled copper foil obtained, or make evaluations FPC, for the evaluation of Young's modulus described later, crystal boundary length, stress mitigation rate, bendability (continuous bend, intermittently bend).Obtained result is summarized in table 1 and table 2.But about embodiment 2 and comparative example 2, not stacked polyimide and tectum (cover lay) and make its lamination process machine by roll temperature being adjusted to 350 DEG C, anneal thus, carry out the thermal treatment same with the thermal treatment of the situation making evaluation FPC described later.At this moment heat treatment time was set to for 1 second.
[Young's modulus]
Young's modulus uses resonant mode tester (Japanese technoplas Co., Ltd. TE-RT) to measure.
[crystal boundary length]
CP(Cross section polisher is used to the Copper Foil after above-mentioned condition (200 DEG C or 350 DEG C) annealing, section polishing) and form rolling parallel sections, use EBSD(Electron Back Scattering Diffraction, EBSD, Jeol Ltd. JXA8500F), with step-length 0.5 μm, acceleration voltage 15kV, WD23mm, electric current 5 × 10
-8a is to range of observation 1000 μm
2crystalline orientation measure.The situation being more than 15 degree by the crystalline orientation difference with adjacent measuring point regards crystal grain boundary as, is determined at the crystal grain boundary length comprised in range of observation.
[stress mitigation rate]
Use precision cutting tool the rolled copper foil of acquisition to be cut into the strip of width 12.7mm, anneal with above-mentioned condition (200 DEG C or 350 DEG C), use tensile testing machine (Shimadzu Scisakusho Ltd AGS-X) to be fixed with chuck spacing 50mm.Afterwards, chuck spacing is stretched to 50.1mm(and is equivalent to 0.2% distortion), the change of load is determined at 25 DEG C.As stress mitigation rate (%), obtain the stress T will obtained after t hour
twith the stress T of initial (after 0 hour)
0difference divided by initial stress T
0after value { (T
0-T
t)/T
0.Stress mitigation rate (%) when t=5 hour is shown in table 2.
[bendability evaluation]
Thermo-compressed (200 DEG C, 30 points) is carried out to the Copper Foil obtained with rolling processing and polyimide film (nikkan Industrial Co., Ltd NIKAFLEX: polyimide thickness 12.5 μm, caking agent thickness 15 μm), obtains copper-clad laminated board.The copper-clad laminated board obtained is etched, make the FPC of circuit width 100 μm, afterwards by tectum (nikkan Industrial Co., Ltd NIKAFLEX: polyimide thickness 12.5 μm, caking agent thickness 15 μm) thermo-compressed (200 DEG C, 30 points) to circuit face, system is evaluated uses FPC.But about embodiment 2 and comparative example 2, Use Adjustment is the lamination process machine of roll temperature 350 DEG C, the Copper Foil obtained with rolling processing and above-mentioned polyimide film are made copper-clad laminated board, use after gimmick similar to the above makes FPC, Use Adjustment is that above-mentioned overlaminate is received circuit face by the lamination process machine of roll temperature 350 DEG C, and system is evaluated uses FPC.Further, it was 1 second that heat-up time at this moment adds up to.
Sliding velocity is set to per minute 120 times by pliability test, carries out in room temperature environment.Consistent to the distortion of Copper Foil applying during in order to make bending, bending radius is set to 1.5mm when copper thickness is 18 μm, when 12 μm, be set to 1.0mm, when 9 μm, be set to 0.75mm, evaluate with the number of times to fracture respectively.To test portion energising, cut off by conducting and detect fracture.In continuous bend, if if breaks are less than 100,000 times, be ×, if more than 100,000 times is then zero less than 300,000 times, if be then ◎ for more than 300,000 times.During this external interval is bending, carries out 1000 times continuously with 5 h apart and bend, if if breaks are less than 50,000 times, be ×, if more than 50,000 times is then zero less than 100,000 times, if be then ◎ for more than 100,000 times.
[table 1]
[table 2]
Industry utilizes possibility
According to the present invention, the bending tolerance Copper Foil of interval can be obtained, can obtain when using in FPC in the goods of reality for bending rolled copper foil, copper-clad laminated board, the flexible printing wiring board (FPC) with higher weather resistance.Possessing interval of the present invention in use bends in the electronics of flexible printing wiring board (FPC) of tolerance Copper Foil, because the FPC becoming its movable part possesses the bending tolerance of the behaviour in service in the goods reflecting reality, so compared with the existing goods only considered the tolerance that continuous print bends, weather resistance, of superior reliability.The present invention is invention useful in industry.
Claims (12)
1. interval bends a tolerance Copper Foil,
Stress in bending relaxes, relative in 25 DEG C 0.2% distortion, meet the condition of formula I below:
(T
0-T
5)/T
0≤ 25(%) (formula I)
Wherein, T
0represent initial stress, T
5represent the stress after 5 hours,
Wherein, Copper Foil is:
By copper and impurity can not be kept away, also to add up to 20 ~ 500 quality ppm to contain the Copper Foil formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed; Or
By outside oxygen free copper or tough pitch copper also to add up to 20 ~ 500 quality ppm to be added with the Copper Foil formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed.
2. interval according to claim 1 bends tolerance Copper Foil, observes from rolling parallel sections, often observes sectional area 1000 μm
2the length of crystal grain boundary be less than 200 μm.
3. interval according to claim 1 bends tolerance Copper Foil, has the Young's modulus of the scope of 60 ~ 105GPa.
4. interval according to claim 1 bends tolerance Copper Foil, and Copper Foil is rolled copper foil.
5. interval according to claim 1 bends tolerance Copper Foil, and Copper Foil is with the rolled rolled copper foil of degree of finish more than 96%.
6. interval according to claim 1 bends tolerance Copper Foil, is layered in flexible printing wiring board.
7. a Copper Foil, carry out with 160 ~ 400 DEG C 1 second ~ heat treated of 1 hour after, the interval described in any one becoming claim 1 ~ 7 bends tolerance Copper Foil.
8. a Copper Foil, is carrying out the heat treated of 30 minutes with 200 DEG C, or after carrying out the heat treated in 1 second with 350 DEG C, the interval described in any one becoming claim 1 ~ 6 bends tolerance Copper Foil.
9. a flexible printing wiring board, the interval described in any one being laminated with claim 1 ~ 6 bends tolerance Copper Foil and forms.
10. the interval described in manufacturing claims 1 bends a manufacture method for tolerance Copper Foil, comprises:
The operation of the ingot casting of casting copper;
The ingot casting of copper is carried out to the operation of hot rolling;
The ingot casting of the copper to hot rolling carries out the operation of the cold rolling and annealing of more than 1 time; And
The mode being more than 96% with total degree of finish and final rolling degree of finish carries out the last cold rolling operation for making finished product thickness, wherein, carries out in the operation of cold rolling and annealing of more than 1 time at the ingot casting of the copper to hot rolling,
The annealing finally carried out is carried out with the heat-up rate of more than 5 DEG C/sec less than 40 DEG C/sec,
Wherein, the ingot casting of copper is:
By containing copper and impurity can not be kept away, also with the ingot casting adding up to 20 ~ 500 quality ppm to contain the copper formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed; Or
By outside oxygen free copper or tough pitch copper also with the ingot casting adding up to 20 ~ 500 quality ppm to be added with the copper formed from the element by more than a kind that selects the group that Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B and V are formed.
11. manufacture method according to claim 10, carry out in the operation of cold rolling and annealing of more than 1 time at the ingot casting of the copper to hot rolling,
The annealing finally carried out carry out slightly before cold rolling with 60% ~ 90% degree of finish and total degree of finish carry out.
12. 1 kinds of intervals bend the manufacture method of tolerance Copper Foil, comprise: to the rolled copper foil manufactured by the manufacture method described in claim 10 or 11 with 160 ~ 400 DEG C carry out 1 second ~ operation of heat treated of 1 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-089363 | 2012-04-10 | ||
| JP2012089363 | 2012-04-10 |
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| JP (2) | JP5826160B2 (en) |
| KR (1) | KR20130115140A (en) |
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| JP5826160B2 (en) * | 2012-04-10 | 2015-12-02 | Jx日鉱日石金属株式会社 | Rolled copper foil, copper-clad laminate, flexible printed wiring board and manufacturing method thereof |
| JP6294257B2 (en) * | 2015-03-30 | 2018-03-14 | Ｊｘ金属株式会社 | Copper alloy foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| KR101721314B1 (en) * | 2015-05-21 | 2017-03-29 | 제이엑스금속주식회사 | Rolled copper foil, copper clad laminate, and flexible printed board and electronic device |
| CN111526674A (en) * | 2015-06-05 | 2020-08-11 | Jx日矿日石金属株式会社 | Rolled copper foil, copper-clad laminate, flexible printed board, and electronic device |
| JP6578780B2 (en) * | 2015-07-17 | 2019-09-25 | 大日本印刷株式会社 | Laminate for touch panel and foldable image display device |
| WO2017014198A1 (en) | 2015-07-17 | 2017-01-26 | 大日本印刷株式会社 | Laminate for optical members and image display device |
| JP7016603B2 (en) * | 2015-07-17 | 2022-02-07 | 大日本印刷株式会社 | Hard-coated film for touch panels and foldable image display device |
| JP7016602B2 (en) * | 2015-07-17 | 2022-02-07 | 大日本印刷株式会社 | Hard-coated film for touch panels and foldable image display device |
| JP7016605B2 (en) * | 2015-07-17 | 2022-02-07 | 大日本印刷株式会社 | Laminated body for touch panel and foldable image display device |
| JP7016604B2 (en) * | 2015-07-17 | 2022-02-07 | 大日本印刷株式会社 | Laminated body for touch panel, foldable image display device |
| JP6392268B2 (en) * | 2016-02-05 | 2018-09-19 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| JP6294376B2 (en) * | 2016-02-05 | 2018-03-14 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| JP6328679B2 (en) * | 2016-03-28 | 2018-05-23 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| JP6617313B2 (en) * | 2017-08-03 | 2019-12-11 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| JP6774457B2 (en) * | 2018-05-16 | 2020-10-21 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices |
| JP6827022B2 (en) * | 2018-10-03 | 2021-02-10 | Ｊｘ金属株式会社 | Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices |
| WO2020138283A1 (en) * | 2018-12-28 | 2020-07-02 | デンカ株式会社 | Ceramic-copper composite, ceramic circuit board, power module, and method for manufacturing ceramic-copper composite |
| CN114269957B (en) * | 2019-09-27 | 2022-07-29 | 三菱综合材料株式会社 | Pure copper plate |
| JP7238872B2 (en) * | 2020-09-09 | 2023-03-14 | 大日本印刷株式会社 | HARD COAT FILM FOR TOUCH PANEL AND FOLDABLE IMAGE DISPLAY DEVICE |
| JP7238869B2 (en) * | 2020-09-09 | 2023-03-14 | 大日本印刷株式会社 | Laminate for touch panel, foldable image display device |
| JP7238870B2 (en) * | 2020-09-09 | 2023-03-14 | 大日本印刷株式会社 | LAMINATED BODY FOR TOUCH PANEL AND FOLDABLE IMAGE DISPLAY DEVICE |
| JP7238871B2 (en) * | 2020-09-09 | 2023-03-14 | 大日本印刷株式会社 | HARD COAT FILM FOR TOUCH PANEL AND FOLDABLE IMAGE DISPLAY DEVICE |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI491325B (en) | 2015-07-01 |
| JP2013234383A (en) | 2013-11-21 |
| CN103361509A (en) | 2013-10-23 |
| TW201343014A (en) | 2013-10-16 |
| KR20130115140A (en) | 2013-10-21 |
| JP5826160B2 (en) | 2015-12-02 |
| JP2015061950A (en) | 2015-04-02 |
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