CN109392242A - Flexible printed base plate copper foil, the copper clad layers stack for having used the copper foil, flexible printed base plate and electronic equipment - Google Patents
Flexible printed base plate copper foil, the copper clad layers stack for having used the copper foil, flexible printed base plate and electronic equipment Download PDFInfo
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- CN109392242A CN109392242A CN201810877181.4A CN201810877181A CN109392242A CN 109392242 A CN109392242 A CN 109392242A CN 201810877181 A CN201810877181 A CN 201810877181A CN 109392242 A CN109392242 A CN 109392242A
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- copper foil
- base plate
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- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000011889 copper foil Substances 0.000 title claims abstract description 98
- 239000010949 copper Substances 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 14
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005097 cold rolling Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 23
- 239000013078 crystal Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 238000009825 accumulation Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000001953 recrystallisation Methods 0.000 description 12
- 238000001887 electron backscatter diffraction Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 239000007767 bonding agent Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 210000002469 basement membrane Anatomy 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of bendability excellent flexible printed base plate copper foil.A kind of flexible printed base plate copper foil, it is the copper foil comprising the Cu of 99.0 mass % or more and the inevitable impurity of surplus, the conductivity of the copper foil is more than 75%IACS, and composition ratio=(the region A that KAM value is 0~0.875)/(the region B that KAM value is 0~5) of the KAM value of copper foil surface is 0.98 or more.
Description
Technical field
The present invention relates to the copper foil for the wiring part for being suitable for flexible printed base plate etc., the copper-clad laminated of the copper foil is used
Body, flexible wiring plate and electronic equipment.
Background technique
Flexible printed base plate (flexible wiring plate, hereinafter referred to as " FPC ") is widely used in electronic circuit because having flexibility
Bending section or movable part.For example, in the movable part or fold type portable telephone of the disks relevant device such as HDD or DVD and CD-ROM
Bending section etc. use FPC.
FPC refers to (Copper Clad Laminate, following by the copper clad layers stack that obtains copper foil and laminated resin
Referred to as CCL) etching and formed wiring, again be referred to as coating resin layer cladding thereon obtained from substrate.It is covered in stacking
The last stage of cap rock, a ring of the surfaction process as the adhesiveness for improving copper foil and coating carry out copper foil table
The etching in face.In addition, also will do it thin-walled etching sometimes to reduce the thickness of copper foil to improve bendability.
However, with the small-sized, slim of electronic equipment, high performance, it is desirable that pacified in the inside of these equipment with high density
FPC is filled, in order to carry out high-density installation, then needs for FPC to be bent inside the equipment for being accommodated in miniaturization, i.e. demanding bending
Property.
On the other hand, a kind of copper foil (patent document for improving high circulation bendability representated by IPC bendability is developed
1、2)。
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-100887 bulletin；
Patent document 2: Japanese Unexamined Patent Publication 2009-111203 bulletin.
Summary of the invention
Problems to be solved by the invention
However, as described above, need to improve bendability representated by MIT folding resistance in order to high-density installation FPC, previous
Copper foil has that the improvement of bendability is still insufficient.
The present invention proposes in order to solve the above problems, its object is to: provide a kind of bendability excellent flexible printing
Base board-use copper-clad, the copper clad layers stack for having used the copper foil, flexible printed base plate and electronic equipment.
Means for solving the problems
Present inventor has performed various researchs, as a result, it has been found that: it is miniaturize by the crystal particle diameter before the final cold rolling by copper foil, it is cold
The accumulation for rolling the middle indexing to each region of copper foil becomes uniformly, even if straining also equal in any region of copper foil after re-crystallization
It is opened, therefore the reduction of KAM value and the raising of elongation at break can be had both, and then bendability can be improved.In general,
KAM value is bigger, then intragranular strain is more accumulated after re-crystallization, region and KAM value in KAM value big (accumulation of intragranular strain is big)
The region of small accumulation of strain (intragranular few) is broken due to plastic deformation behavior when bending is different.Therefore, if increasing KAM
It is worth small region, then plastic deformation behavior when bending in copper foil becomes uniformly, and bendability improves.
That is, flexible printed base plate of the invention with copper foil be comprising 99.0 mass % or more Cu and surplus it is inevitable
Impurity copper foil, conductivity is more than 75%IACS, the composition ratio of the KAM value of above-mentioned copper foil surface=(KAM value is 0~0.875
Region A)/(the region B that KAM value is 0~5) be 0.98 or more.
In flexible printed base plate copper foil of the invention, by plate thickness be set as x [μM] when, preferably elongation at break y [%] is
Formula 1:[y=- 0.0365 (% (μm)-2)x2+2.1352(%·(μm)-1) x -5.7219 (%)] more than.
In flexible printed base plate copper foil of the invention, the tough pitch copper standardized in JIS-H3100 (C1100) is preferably comprised
(TPC) or the oxygen-free copper (OFC) of JIS-H3100 (C1020).
In flexible printed base plate copper foil of the invention, preferably also individually or it is two or more containing element below and
The copper foil of formation: 0.03 mass % P below, 0.05 mass % Ag below, 0.14 mass % Sb below, 0.163 mass % with
Under Sn, 0.288 mass % Ni below, 0.058 mass % Be below, 0.812 mass % Zn below, 0.429 mass % with
Under In and 0.149 mass % Mg below.
Flexible printed base plate of the invention is rolled copper foil with copper foil, and annealing in preferably 300 DEG C × 30 minutes (wherein, heats up
Speed is 100 DEG C/min~300 DEG C/min) after, conductivity is more than 75%IACS, and above-mentioned composition ratio is 0.98 or more.
Copper clad layers stack of the invention is to form above-mentioned flexible printed base plate copper foil and resin layer stackup.
Flexible printed base plate of the invention is to form circuit on the above-mentioned copper foil of above-mentioned copper clad layers stack and constitute.
Electronic equipment of the invention is formed using above-mentioned flexible printed base plate.
Invention effect
According to the present invention, the excellent flexible printed base plate copper foil of bendability can be obtained.
Brief description
[Fig. 1] is the figure for showing the relationship of copper thickness and elongation at break of embodiment and comparative example.
[Fig. 2] is the figure for showing the crystal orientation distribution (map) of embodiment and comparative example measured by EBSD.
Specific embodiment
Hereinafter, being illustrated to the embodiment of copper foil according to the present invention.It should be noted that in the present invention,
Unless otherwise specified, then " % " expression " quality % ".
< forms >
Copper foil according to the present invention includes the Cu of 99.0 mass % or more and the inevitable impurity of surplus.
As described above, being miniaturize by the crystal particle diameter before the final cold rolling by copper foil, to each region of copper foil in cold rolling
The accumulation of indexing becomes uniformly, even if strain is also opened, therefore can be simultaneous after re-crystallization in any region of copper foil
Have the reduction of KAM value and the raising of elongation at break, and then bendability improves.In general, KAM value is bigger, then grain after re-crystallization
Internal strain is more accumulated, in the region of KAM value big (accumulation of intragranular strain is big) and the area of KAM value small (accumulation of intragranular strain is few)
Domain is broken due to plastic deformation behavior when bending is different.Therefore, if increasing the small region of KAM value, not only in copper foil
Plastic deformation behavior when bending becomes uniformly, and bendability also improves.
But in the case where the fine copper system composition that above-mentioned Cu is 99.0 mass % or more, due to the recrystallization in copper foil
After be difficult to reduce KAM value, therefore by initial stage in the cold rolling cold rolling of initial stage when annealing and cold rolling is repeated (when) into
Row full annealed, can import processing strain in large quantities by cold rolling, while increasing the small region of KAM value after re-crystallization
Elongation at break is improved, can be further improved bendability.
In addition, being repeated to have both the raising of the reduction of KAM value and elongation at break after the recrystallization of copper foil
Among the process of cold rolling and annealing, the crystal particle diameter before the final cold rolling carried out after final annealing is preferably set as 10μM or more
~less than 15μm.It is 15 in crystal particle diameterμIn the case where m or more, the reduction of KAM value and proposing for elongation at break can not be had both
Height, bendability are deteriorated.It on the other hand, is less than 10 in crystal particle diameterμIn the case where m, reduction and the extension at break of KAM value are had both
The effect of the raising of rate reaches saturation.
Crystal particle diameter before final cold rolling is 15μIn the case where m or more, the entanglement locality of indexing when due to processing
Ground becomes smaller, and reduces the accumulation of strain, therefore strain be not released after re-crystallization, it is difficult to have both the reduction of KAM value
With the raising of elongation at break.Crystal particle diameter before final cold rolling is less than 10μIn the case where m, in the almost entire of copper foil
Indexing when region can all generate processing is tangled, the entanglement that can not be formed in more than it, the KAM value after having both recrystallization reduce and
The effect that elongation at break improves reaches saturation.Moreover, rolling cost increases.Therefore, by the crystal particle diameter before final cold rolling
Lower limit is set as 10μm。
As the method for the crystal particle diameter miniaturization before the final cold rolling by copper foil, it can enumerate: make final annealing temperature
Greater than 400 DEG C and at 500 DEG C or less and the cold rolling processing amount η before final annealing will be set as 0.91 or more and 1.6 or less.
In addition, as the addition element for reducing the KAM value after recrystallization, relative to above-mentioned composition, if individually or two
Kind or more contain element below, then can easily reduce KAM value: 0.0005 mass % or more and 0.03 mass % P below,
0.0005 mass % or more and 0.05 mass % Ag below, 0.0005 mass % or more and 0.14 mass % Sb below, 0.0005
Quality % or more and 0.163 mass % Sn below, 0.0005 mass % or more and 0.288 mass % Ni below, 0.0005 mass %
Above and 0.058 mass % Be below, 0.0005 mass % or more and 0.812 mass % Zn below, 0.0005 mass % or more
And 0.429 mass % In and 0.0005 mass % or more below and 0.149 mass % Mg below.
Since P, Ag, Sb, Sn, Ni, Be, Zn, In and Mg will increase the entanglement frequency of indexing in cold rolling, tying again
The reduction of KAM value and the raising of elongation at break can be had both after crystalline substance.In addition, if the initial stage in cold rolling only once weighed
Recrystallization annealing temperature no longer carries out full annealed later, then increases the entanglement of indexing by cold rolling, thus import processing in large quantities
Strain, and then the reduction of KAM value and the raising of elongation at break can be more easily had both after re-crystallization.
If containing have more than the P of 0.03 mass %, the Ag more than 0.05 mass %, more than the Sb of 0.14 mass %, more than 0.163
The Sn of quality %, the Ni more than 0.288 mass %, the Be more than 0.058 mass %, more than the Zn of 0.812 mass %, more than 0.429
The In of quality % or Mg more than 0.149 mass % then exists since conductivity reduces and is not suitable as flexible base board-use copper-clad
The case where, therefore above range is set as the upper limit.The lower limit of the content of P, Sb, Sn, Ni, Be, Zn, In and Mg is not limited especially
System, but be for example industrially difficult to control each element less than 0.0005 mass %, therefore can be by the content of each element
Lower limit is set as 0.0005 mass %.
Copper foil according to the present invention can be to include the tough pitch copper (TPC) or JIS- that are standardized in JIS-H3100 (C1100)
The composition of the oxygen-free copper (OFC) of H3100 (C1020).
Furthermore it is possible to contain composition obtained by P relative to above-mentioned TPC or OFC.
The composition ratio > of < KAM value
The composition ratio of the KAM value of copper foil surface=(region that KAM value is 0~0.875)/(region that KAM value is 0~5) is 0.98
More than.
KAM value is index obtained from gun parallax between the adjacent measuring point in quantitative crystal grain, if KAM value is big, intragranular
The accumulation of strain is big, if KAM value is small, the small tendency of the accumulation in intragranular strain.
Use (KAM value for 0~0.875 region A)/(the region B that KAM value is 0~5) as the composition ratio of KAM value
Reason for this is that: region B indicates the definition of intragranular strain, wherein and in the region A of " 0~0.875 ", the accumulation of intragranular strain is few,
Be difficult to become bending when crackle (crack) starting point, in contrast, " the region region B- B " (more than 0.875 and 5 with
Under) in, the accumulation of intragranular strain is big, easily becomes the starting point of crackle when bending.
If the composition ratio of above-mentioned KAM value is 0.98 or more, since the big region of the accumulation of intragranular strain is few, crackle
Starting point it is few, bendability improve.
KAM value using EBSD (electron backscatter diffraction: electron backscatter diffraction) by being surveyed
Sample surface and acquire.EBSD can be according to the crystal orientation of nm grades of resolution measurement near sample surface, can be by surveying
Fixed number is according to the variation for calculating local crystal orientation (local azimuthal is poor).Moreover, according to these EBSD data, by adjacent measuring point
Between KAM value (gun parallax) be that 0 ° or more and 5 ° of boundaries below are considered as intragranular accumulation and strain.
It should be noted that position of the KAM value (gun parallax) greater than 5 ° is crystal boundary, it is different from intragranular and strains.
< elongation at break >
By plate thickness be set as x [μM] when, preferably elongation at break y [%] be formula 1:[y=- 0.0365 (% (μm)-2)x2+2.1352(%・
(μm)-1) x-5.7219 (%)] more than.
The elongation of copper foil changes according to thickness, and the more thick then elongation of thickness is bigger.Therefore, bendability depends on and copper
The corresponding elongation of foil thickness.Therefore, in order to improve bendability, the absolute value of the elongation of regulation copper foil is not only needed, also
Need the relationship of regulation elongation and thickness.The present invention is to be conceived to the relationship of elongation and thickness in this way.
Fig. 1 shows the thickness of aftermentioned embodiment 1~16 and comparative example 1~6 and the relationship of elongation at break.Such as Fig. 1 institute
Show, compared with the group of Examples 1 to 7, the group of embodiment 8~12 is small the elongation at break under same thickness.In addition, with
When same thickness is observed, the elongation at break of all embodiments 1~16 is all larger than the group of comparative example (comparative example 1~6)
Elongation at break.
It is thus regarded that: if elongation at break is the region to become larger, bendability (MIT folding number) compared with comparative example
Also excellent, as compared with comparative example elongation at break be the minimum to become larger value (lower limit), found out using least square method
Pass through the approximate conic section of each plot point of the group of embodiment 8~12, the elongation at break of the group of the embodiment 8~12
Less than the group of Examples 1 to 7.As a result, having obtained above-mentioned formula 1 shown in the dotted line of Fig. 1.
It should be noted that since Examples 1 and 2 overlapping, embodiment 6 and 7 are overlapped, so the plot point of Examples 1 to 7
Number be 5 rather than 7.
As known from the above: if elongation at break y [%] is the region S (referring to Fig.1) of 1 or more formula, bendability is excellent.
For example, being 12 in copper thicknessμIn the case where m, elongation at break (%) and bendability are (secondary) as follows respectively: implementing
Example 4 (: 35%:452 times), embodiment 10 (: 15%:352 times), comparative example 4 (: 12%:188 times), compared with comparative example 4, embodiment
4 and 10 bendability is excellent, and embodiment 4 is most excellent.
It should be noted that formula 2:[y=- 0.07625 (% (μm)-2)x2+4.4090(%・(μm)-1) x-7.5054(%)]
It is to be found out obtained from the approximate conic section of each plot point of Examples 1 to 7 using least square method as a result, the reality
Apply example 1~7 be compared with the group of embodiment 8~12 under same thickness the big group of elongation at break.
Certainly, the higher person of elongation at break is the more preferred, so the copper foil more than the value of formula 2 is also contained in the application hair certainly
In bright range, even if being identical copper thickness, the raising of elongation at break is also limited, therefore finds out formula 2 and be used as its boundary
The illustration of limit.Therefore, as the scope of the present invention is more reliably realized, 1 or more formula and the region S1 below of formula 2 be can also be
(referring to Fig.1), the present invention is not limited to the regions below of formula 2.
If elongation at break is insufficient [y=- 0.0365 (% (μm)-2)x2+2.1352(%・(μm)-1) x -5.7219 (%)], then
Since when being bent flexible printed base plate, copper foil can not follow the elongation of resin, bendability is poor, so being not suitable for flexible print
Brush substrate purposes.
In addition, about will be disconnected after copper foil progress annealing in 300 DEG C × 30 minutes (heating rate is 100~300 DEG C/min)
It splits elongation y [%], in preferably also above-mentioned range.
< tensile strength (TS), elongation at break >
About tensile strength and elongation at break, by the tension test according to IPC-TM650, in the wide 12.7mm of test film, room
Under warm (15~35 DEG C), tensile speed 50.8mm/ minutes, gauge length 50mm, along parallel with the rolling direction of copper foil
Direction carries out tension test.
< 30 minutes heat treatment > at 300 DEG C
Copper foil according to the present invention is used for flexible printed base plate, at this point, CCL obtained from laminated copper foil and resin due to
Resin solidification is treated with heat such that at 200~400 DEG C, therefore by recrystallizing there is a possibility that crystal grain becomes thick.
Therefore, before and after with laminated resin, the composition ratio of the KAM value of copper foil changes.Therefore, involved in the present invention
Flexible printed base plate with copper foil define with after the copper clad layers stack, solidification that receives resin heat is formed after laminated resin
The copper foil of the state of processing.That is, due to having received heat treatment, so being the copper foil for not carrying out the state of new heat treatment.
On the other hand, flexible printed base plate according to the present invention with copper foil define to the copper foil before laminated resin into
State when the above-mentioned heat treatment of row.Heat treatment in 30 minutes, which has been imitated, at this 300 DEG C solidifies resin in the stacking of CCL
The temperature condition of heat treatment.It should be noted that the oxidation of the copper foil surface caused by being heat-treated in order to prevent, the ring of heat treatment
The preferred reproducibility in border or non-oxidizing environment, as long as such as vacuum environment or argon, nitrogen, hydrogen, carbon monoxide etc. or by
The environment etc. that these mixed gas are constituted.As long as heating rate is between 100~300 DEG C/min.
Copper foil of the invention can for example be operated as follows and be manufactured.Firstly, copper ingot dissolution, casting are carried out heat later
It rolls, cold rolling and annealing, the initial stage preferably in cold rolling carries out full annealed, while carrying out above-mentioned final cold rolling, thus may be used
With manufacturing copper foil.
Here, if by (referring in the entire process that cold rolling and annealing is repeated, after the final anneal before final cold rolling
The cold rolling carried out) crystal particle diameter miniaturize to 10μM or more and less than 15μM can then control the composition ratio of KAM value
0.98 or more.
< copper clad layers stack and flexible printed base plate >
In addition, being carried out to copper foil of the invention: (1) resin precursor (such as the polyimide precursor for being known as varnish) being cast and added
Heat be allowed to polymerize and (2) using with basement membrane thermoplastic adhesive of the same race on copper foil of the invention laminated basement membrane, thus
To the copper clad layers stack (CCL) being made of this 2 layers of copper foil and resin base material.In addition, passing through painting laminated on copper foil of the invention
There is the basement membrane of bonding agent, the available copper clad layers stack (CCL) being made of copper foil, resin base material and this 3 layers of adhesive layer therebetween.
When manufacturing these CCL, heat treatment is carried out to copper foil and is allowed to recrystallize.
Circuit is formed on them using photoetching technique, as needed circuit is implemented to be electroplated, then laminated cover film, by
Flexible printed base plate (flexible wiring plate) can be obtained in this.
Therefore, copper clad layers stack of the invention is to form copper foil and resin layer stackup.In addition, of the invention is flexible
Printed base plate is to form circuit on the copper foil of copper clad layers stack and constitute.
It as resin layer, can enumerate: PET (polyethylene terephthalate), PI (polyimides), LCP (polymerizable mesogenic
Object), PEN (polyethylene naphthalate), but it is not limited to this.In addition, their resin film can be used as resin layer.
As the laminating method of resin layer and copper foil, can be coated with to form the material of resin layer and heated in copper foil surface
Film forming.In addition, it is possible to use resin film uses bonding agent below as resin layer between resin film and copper foil, can also
Resin film hot pressing is connected on copper foil without using bonding agent.Wherein, the angle for never applying extra heat to resin film goes out
Hair is, it is preferable to use bonding agent.
In the case where using film as resin layer, which can be laminated on copper foil across adhesive layer.At this point, excellent
Choosing uses the bonding agent with film identical component.For example, in the case where using polyimide film as resin layer, adhesive layer
It is preferable to use polyimides system bonding agents.Still it should be noted that, polyimide adhesive mentioned here refers to comprising acid imide
The bonding agent of key further includes polyetherimide etc..
It should be noted that present invention is not limited to the embodiments described above.As long as in addition, playing effect effect of the invention
Fruit, the copper alloy in above embodiment can also contain other compositions.In addition, can also be electrolytic copper foil.
For example, the surface treatment of roughening treatment, antirust treatment, resistance to heat treatment or their combinations can be implemented to copper foil surface.
Embodiment
Next, enumerating embodiment to illustrate the present invention in further detail, however, the present invention is not limited to these examples.
It adds element shown in table 1 respectively in cathode copper to form forming for table 1, is cast in Ar environment, obtained ingot bar.
Oxygen content in ingot bar is less than 15ppm.The ingot bar is subjected to hot rolling at 900 DEG C after homo genizing annelaing, carries out cold rolling later, then into
Row 1 time annealing, crystal particle diameter is adjusted to 10μM or more and less than 15μm。
Later, the oxide skin that surface generates is removed, final cold rolling is carried out with degree of finish η shown in table 2, obtains target most
The foil of whole thickness.The heat treatment for carrying out 300 DEG C × 30 minutes to gained foil under argon environment, has obtained copper foil sample.Heat treatment
Copper foil afterwards has imitated the state that heat treatment is received in the stacking of CCL.
The evaluation > of < A. copper foil sample
1. conductivity
25 DEG C of conductivity is determined by 4 terminal methods according to JIS H 0505 for each copper foil sample after above-mentioned heat treatment
(%IACS)。
If conductivity is greater than 75%IACS, electric conductivity is good.
2. tensile strength and elongation at break
It is wide in test film by the tension test according to IPC-TM650 for each copper foil sample after above-mentioned heat treatment
Under 12.7mm, room temperature (15~35 DEG C), tensile speed 50.8mm/ minutes, gauge length 50mm, along the rolling direction with copper foil
Parallel direction carries out tension test, thus determines tensile strength and elongation at break.
3.KAM value
For the surface of each sample after above-mentioned heat treatment, using EBSD, (OIM of TSL Solutions company manufacture (is oriented
As microscope, Orientation Imaging Microscopy)) device carried out EBSD measurement.Measurement voltage is set as 15kV,
Focal length is set as 17mm, and sample inclination angle is set as 70 °.Measuring the visual field is 25μm×25μ5 positions of m measure spacing d=0.2μm。
The incidental analysis software of use device (OIM analysis5) analyzes resulting EBSD data, has calculated KAM value
Composition ratio=(KAM value 0~0.875)/(KAM value 0~5).When carrying out data analysis, CI value (secrecy index
(Confidential Index)) it is 0.05 data below, it is removed from analysis due to precision is low.
If the composition ratio of KAM value is 0.98 or more, the accumulation of intragranular strain is small.
4. the bendability (MIT folding resistance) of copper foil
For each copper foil sample after above-mentioned heat treatment, (the round-trip bending time of MIT folding number is determined according to JIS P 8115
Number).Wherein, the R for being bent tool is set as 0.38mm, loading is set as 250g.
If MIT folding number is greater than the comparative example of same thickness, the bendability of copper foil is good.
5. crystal particle diameter
Before above-mentioned heat treatment, each sample (after final annealing) before final cold rolling is observed using SEM (scanning electron microscope),
Average grain diameter has been found out according to JIS H 0501.Wherein, twin crystal is considered as respective crystal grain and is determined.Measurement region be set as with
The 400 of the parallel section of rolling directionμm ×400μm。
Acquired results are shown in Table 1, table 2.
[table 1]
[table 2]
From table 1, table 2: in the case where the composition ratio of KAM value is 0.98 or more each embodiment, MIT bendability is more identical
The comparative example of thickness is excellent.
On the other hand, final annealing temperature is as follows greater than 500 DEG C of result: the crystal particle diameter before final cold rolling is 15μm
In the case where above comparative example 1~6,9,10, the composition ratio of KAM value is each compared with same thickness less than 0.98, MIT bendability
Embodiment is poor.
In addition, conductivity is 75% hereinafter, poorly conductive in the case where the additive amount of P is more than 0.03% comparative example 7.
In the case where comparative example 8 of the Cu less than 99.0 mass %, conductivity is also 75% hereinafter, poorly conductive.
In Fig. 2, the crystal orientation distribution (map) of embodiment 2 and comparative example 10 measured by EBSD is shown.Fig. 1
Dark portion be " KAM value be 0~0.875 " region, and highlights is " the KAM value be more than 0.875 and below 5 " in addition to dark portion
Region.Known to: compared with comparative example 10, the dark portion of embodiment 2 is more, and the composition ratio of KAM value is higher than comparative example 10.
Claims (8)
1. flexible printed base plate copper foil is the copper comprising the Cu of 99.0 mass % or more and the inevitable impurity of surplus
Foil,
The conductivity of the copper foil is more than 75%IACS,
The composition ratio of the KAM value of above-mentioned copper foil surface=(the region A that KAM value is 0~0.875)/(the region B that KAM value is 0~5)
It is 0.98 or more.
2. flexible printed base plate copper foil described in claim 1, by plate thickness be set as x [μM] when, elongation at break y [%] is formula
1:[y=- 0.0365 (% (μm)-2)x2+2.1352(%・(μm)-1) x -5.7219 (%)] more than.
3. flexible printed base plate copper foil of any of claims 1 or 2, which includes to be standardized in JIS-H3100 (C1100)
Tough pitch copper or JIS-H3100 (C1020) oxygen-free copper.
4. described in any item flexible printed base plate copper foils of claims 1 to 3, the copper foil be also individually or two kinds with
Upper to be formed containing element below: 0.03 mass % P below, 0.05 mass % Ag below, 0.14 mass % are below
Sb, 0.163 mass % Sn below, 0.288 mass % Ni below, 0.058 mass % Be below, 0.812 mass % are below
Zn, 0.429 mass % In below and 0.149 mass % Mg below.
5. described in any item flexible printed base plate copper foils of Claims 1 to 4, above-mentioned copper foil is rolled copper foil,
After annealing in 300 DEG C × 30 minutes, conductivity is more than 75%IACS, and above-mentioned composition ratio is 0.98 or more, wherein heating
Speed is 100 DEG C/min~300 DEG C/min.
6. copper clad layers stack, be by the described in any item flexible printed base plate copper foils and resin of Claims 1 to 5 layer by layer
It is folded and formation.
7. flexible printed base plate is to form circuit on the above-mentioned copper foil of copper clad layers stack as claimed in claim 6 and constitute
's.
8. electronic equipment is the electronic equipment for having used flexible printed base plate as claimed in claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017150627A JP6617313B2 (en) | 2017-08-03 | 2017-08-03 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
| JP2017-150627 | 2017-08-03 |
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| Publication Number | Publication Date |
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| CN109392242A true CN109392242A (en) | 2019-02-26 |
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| CN201810877181.4A Active CN109392242B (en) | 2017-08-03 | 2018-08-03 | Copper foil for flexible printed board, copper-clad laminate using same, flexible printed board, and electronic device |
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| Country | Link |
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| JP (1) | JP6617313B2 (en) |
| KR (1) | KR102098479B1 (en) |
| CN (1) | CN109392242B (en) |
| TW (1) | TWI687526B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210689A (en) * | 2019-07-10 | 2021-01-12 | 捷客斯金属株式会社 | Copper foil for flexible printed substrate |
| CN115735018A (en) * | 2020-06-30 | 2023-03-03 | 三菱综合材料株式会社 | Copper alloy, copper alloy plastic working material, electronic/electric device module, terminal, bus bar, lead frame, and heat dissipating substrate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7078070B2 (en) * | 2020-06-30 | 2022-05-31 | 三菱マテリアル株式会社 | Copper alloys, copper alloy plastic processed materials, parts for electronic and electrical equipment, terminals, bus bars, lead frames |
| JP7078091B2 (en) * | 2020-10-29 | 2022-05-31 | 三菱マテリアル株式会社 | Copper alloys, copper alloy plastic processed materials, parts for electronic and electrical equipment, terminals, bus bars, lead frames, heat dissipation boards |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN109392242B (en) | 2021-03-23 |
| KR102098479B1 (en) | 2020-04-07 |
| TW201920699A (en) | 2019-06-01 |
| JP6617313B2 (en) | 2019-12-11 |
| KR20190015102A (en) | 2019-02-13 |
| JP2019029605A (en) | 2019-02-21 |
| TWI687526B (en) | 2020-03-11 |
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