CN104582257B - 2 layers of flexible wiring substrate and use its flexible wiring - Google Patents
2 layers of flexible wiring substrate and use its flexible wiring Download PDFInfo
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- CN104582257B CN104582257B CN201410569301.6A CN201410569301A CN104582257B CN 104582257 B CN104582257 B CN 104582257B CN 201410569301 A CN201410569301 A CN 201410569301A CN 104582257 B CN104582257 B CN 104582257B
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- film
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Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
-
- 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
- H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention provides 2 layers of excellent flexible wiring substrate of folding resistance and has used the flexible wiring of 2 layers of flexible wiring substrate.2 layers of flexible wiring with substrate for provided with the substrate metal layer not being made up of by bonding agent on the surface of polyimide film nickel alloy and the substrate metal layer surface set layers of copper laminate structures 2 layers of flexible wiring substrate, wherein, the difference d [(200)/(111)] of the crystallization orientation ratio [(200)/(111)] of the layers of copper obtained before and after the implementation that the folding resistance as defined in JIS C-5016-1994 is tested is more than 0.03, the crystallization orientation degree index in (111) face of the layers of copper is more than 1.2, crystal grain diameter is more than 300nm.
Description
Technical field
The present invention relates to separating out a part for layers of copper by copper galvanoplastic, improve 2 layers of flexible wiring substrate of folding resistance,
And the flexible wiring using 2 layers of flexible wiring substrate.
Background technology
Flexible wiring, it is widely used in the read/write head of hard disk using its bendability, prints the needs of first-class electronic equipment
Bending is so that need the part of warpage, and bending distribution in LCDs etc..
In the manufacture of the flexible wiring, using the flexible wiring of laminated layers of copper and resin bed with substrate (also referred to as
Make " copper-clad laminate ", " FCCL：Flexible Copper Clad Lamination ") carried out by metal covering etch etc.
The method of distribution processing.
This metal covering etch, be with the layers of copper of substrate chemical etching processing is carried out to flexible wiring and should not part
The method of removing.That is, the surface for the part for wanting to leave as conductor wirings in layers of copper of the flexible wiring by the use of substrate, which is set, to be protected
Sheath, chemical etching processing and washing are carried out by etching solution corresponding with copper, by layers of copper should not be partially selectively
Remove, form conductor wirings.
And flexible wiring substrate (FCCL) can be categorized as three layers of FCCL plates (hereinafter referred to as " three layers of FCCL ") and two layers
FCCL plates (are referred to as " two layers of FCCL ").
Three layers of FCCL turn into the structure (copper being bonded in electrolytic copper foil, rolled copper foil on the resin film of substrate (insulating barrier)
Paper tinsel/bond layer/resin film).On the other hand, two layers FCCL layers of copper that turned into laminated or the structure of copper foil and resin film base material
(layers of copper or copper foil/resin film).
Moreover, substantially exist three kinds in above-mentioned two layers of FCCL.
That is, the FCCL formed on the surface of resin film successively plate substrate metal level and layers of copper (is commonly referred to as metallising
Substrate), coating resin film paint forms the FCCL (be commonly referred to as apply print substrate) of insulating barrier, and the laminated resin on copper foil on copper foil
The FCCL (being commonly referred to as laminated substrate) that film forms.
It is that plating forms substrate metal layer and the FCCL of layers of copper successively for the surface of resin film in above-mentioned metallising substrate,
Layers of copper filming can be made, and polyimide film and the flatness at layers of copper interface are high, so, with applying print substrate, laminated substrate
Or three layers of FCCL compare, it is adapted to the pattern sophistication of distribution.
For example, the layers of copper of metallising substrate can be thick come free key-course by dry type plating and galvanoplastic, on the other hand,
Apply print substrate, laminated substrate or three layers of FCCL then makes its thickness etc. be restricted because of used copper foil.
Moreover, for the copper foil used in the distribution of flexible wiring, for example, the side by implementing heat treatment to copper foil
Method (with reference to patent document 1), carry out roll processing method (with reference to patent document 2) come seek raising folding resistance.
But these methods are related to the painting print base in the rolled copper foil and electrolytic copper foil, two layers of FCCL for three layers of FCCL
The processing of the copper foil of plate and laminated substrate itself.
In addition, the folding resistance evaluation of copper foil, industrially uses " JISC-5016-1994 " etc., " ASTMD2176 " rule
Fixed MIT bending resistance curvature experiment (Folding Endurance Test).
In this test, the number of bends untill forming the broken string of the circuit pattern on test film is evaluated, this
The more big then folding resistance of number of bends is better.
The Japanese Unexamined Patent Publication 8-283886 publications of patent document 1
The Japanese Unexamined Patent Publication 6-269807 publications of patent document 2
The content of the invention
It is not passing through on one side at least in resin film base material as 2 layers of flexible wiring substrate of the object of the present invention
Bonding agent and the plating substrate for being sequentially formed with the metal level that inculating crystal layer and copper coating are formed, accordingly, it is difficult to such as prior art
Only copper coating is heat-treated as disclosed in document or implements calendering processing to improve folding resistance, in plating substrate
Wish to produce the excellent plating substrate of folding resistance.
In view of such situation, the present invention provides a kind of folding resistance excellent 2 layers of flexible wiring substrate and flexible wiring
Plate.
The present inventors are in order to solve above-mentioned problem, to the layers of copper that is formed by plating on polyimide resin layer
Folding resistance is studied with keen determination, and results verification crystallizes the change of regiospecific and the increasing of crystal grain diameter to before and after folding resistance experiment
Add the influence to folding resistance result of the test, reach the present invention.
The present invention the 1st invention be, one kind 2 layers of flexible wiring substrate, 2 layers of flexible wiring substrate, for provided with
The substrate metal layer that is not made up of by bonding agent and on the surface of polyimide film nickel alloy and in the substrate metal layer
2 layers of flexible wiring substrate of the laminate structures for the layers of copper that surface is set, it is characterised in that：In JIS C-5016-1994
The crystallization orientation ratio [(200)/(111)] of the layers of copper obtained before and after the implementation of defined folding resistance experiment difference d [(200)/
(111) be] more than 0.03, the crystallization orientation degree index in (111) face of the layers of copper is more than 1.2, crystal grain diameter be 300nm with
On, and then, the layers of copper is by the copper film layer of the surface filming in the substrate metal layer and on the surface of the copper film layer
The copper electrodeposited coating of film forming is formed, the copper electrodeposited coating, from its surface in more than the 10% of thickness thickness range, by based on
The copper for being periodically reversed (periodic reverse) electric current for periodically carrying out the current potential upset of short time is electroplated to be formed,
The copper plating, adds iron ion in copper plating solution and carries out.
The 2nd invention of the present invention is that the thickness of the layers of copper of 2 layers of flexible wiring substrate in the 1st invention is 5 μm~12 μ
m。
The 3rd invention of the present invention is 2 layers of flexible wiring substrate in the 1st and the 2nd invention, the surface roughness of layers of copper,
It it is less than 0.2 μm by arithmetic average roughness Ra.
The 4th invention of the present invention is a kind of flexible wiring, and the flexible wiring is provided with the distribution of laminate structures, should
The distribution of laminate structures possess the substrate metal layer that is made up of on the surface of polyimide film not by bonding agent nickel alloy and
Layers of copper on the surface of the substrate metal layer, it is characterised in that：In the reality that folding resistance as defined in JIS C-5016-1994 is tested
The difference d [(200)/(111)] for applying the crystallization orientation ratio [(200)/(111)] of the front and rear obtained layers of copper is more than 0.03, institute
The crystallization orientation degree index for stating (111) face of layers of copper is more than 1.2 and crystal grain diameter is more than 300nm, and then, the layers of copper by
The copper electrodeposited coating of copper film layer in the surface filming of the substrate metal layer and the surface filming in the copper film layer is formed,
The copper electrodeposited coating, from its surface in more than the 10% of thickness thickness range, by based on periodically carrying out the short time
The copper of periodic reverse of current potential upset electroplate and formed, the copper plating, add iron ion in the copper plating solution and
Carry out.
The 5th invention of the present invention is the flexible wiring substrate in the 4th invention, and the surface roughness of layers of copper presses arithmetic average
Roughness Ra is less than 0.2 μm.
Invention effect
2 layers of flexible wiring of the present invention is laminate structures with substrate, have the surface of polyimide film not by
Bonding agent and the substrate metal layer being made up of nickel alloy, and the layers of copper set on the surface of its substrate metal layer, in JISC-
Specified in 5016-1994 folding resistance test implementation before and after obtained by layers of copper crystallization orientation ratio [(200)/(111)] it
Poor d [(200)/(111)] is more than 0.03, and the crystallization orientation degree index in (111) face of its layers of copper is more than 1.2, and crystal grain is straight
Footpath is more than 300nm, and according to the present invention, the folding resistance of substrate significantly improves, and achieves industrial significant effect.
Brief description of the drawings
Fig. 1 is the schematic cross-section of the 2 layers of flexible wiring substrate made by metallization.
Fig. 2 is to represent the roll-to-roll (roll- by the substrate metal layer of 2 layers of flexible wiring substrate and copper film layer film forming
To-roll) the synoptic diagram of sputtering unit.
Fig. 3 is the continuous plating dress for the roller-to-roller mode for representing to carry out the plating in the manufacture of 2 layers of flexible wiring substrate
The synoptic diagram put.
Fig. 4 is to schematically illustrate the time of PR electric currents and the figure of current density in the present invention.
Embodiment
(1) 2 layer of flexible wiring substrate
First, 2 layers of flexible wiring substrate of the present invention are illustrated.
2 layers of flexible wiring of the present invention with substrate use polyimide film at least one side not by bonding agent and successively
The laminated laminate structures of substrate metal layer and layers of copper, its layers of copper pass through copper film layer and formed with copper electrodeposited coating.
Fig. 1 is the schematic diagram in the section for representing 2 layers of flexible wiring substrate 6 by metallization making.
Resin film substrate 1 uses polyimide film, at least one face of its polyimide film, from polyimide film side
Film forming, laminated is carried out by the order of substrate metal layer 2, copper film layer 3, copper electrodeposited coating 4.By copper film layer 3 and the structure of copper electrodeposited coating 4
Into layers of copper 5.
As used resin film substrate, in addition to polyimide film, polyamide film, polyester can be used
Film, polytetrafluoroethylene film, PPS films, polyethylene naphthanate film, liquid crystal polymer film etc..
Especially, from the viewpoint of mechanical strength, heat resistance, electrical insulating property, preferred polyimide film.
And then, it may be preferable to the above-mentioned resin film substrate that the thickness using film is 12.5~75 μm.
Substrate metal layer 2 is used for ensuring the reliabilities such as adhesion or the heat resistance of the metal level such as resin film substrate and copper.Cause
This, the material of substrate metal layer is selected from any of nickel, chromium or such alloy, if but considering to touch intensity or distribution system
Etching easness when making, then preferably nichrome.
It is with up to below 22 weight % from the weight % of chromium 15 that the composition of its nichrome is more satisfactory, and expects corrosion resistance
Or the lifting of resistance to migration.
Wherein, the nichrome of 20 weight % chromium flows as nichrome, and as the sputter target of magnetic control sputtering plating method
It can be readily available.In addition, in the alloy comprising nickel, chromium, vanadium, titanium, molybdenum, cobalt etc. can be also added.
And then also can the different several nichromes of laminated chromium concn film, composition be provided with nichrome
The substrate metal layer of concentration gradient.
The more satisfactory thickness of substrate metal layer is 3nm~50nm.
If the film of substrate metal layer less than 3nm, can not ensure the adhesion of polyimide film and layers of copper, corrosion resistance or anti-
It is poor in terms of migration.On the other hand, if the thickness of substrate metal layer is more than 50nm, in metal covering etch progress distribution
During processing, the situation for being difficult to substantially remove substrate metal layer is produced.When the removal of substrate metal layer insufficient situation, then have
The worry of a problem that migration of wiring closet.
Copper film layer 3 is mainly made up of copper, and it is 10nm~1 μm that its thickness is more satisfactory.
If the thickness of copper film layer less than 10nm, can not be ensured with electric conductivity during galvanoplastic film forming copper electrodeposited coating, and
Cause bad order during plating.Even if the thickness of copper film layer more than 1 μm, will not also produce 2 layers of flexible wiring substrate
The problem of in quality, but the problem of productivity is not good enough be present.
(2) film build method of substrate metal layer and copper film layer
Substrate metal layer and copper film layer are preferably formed by dry type plating.
In dry type plating, sputtering method, ion plating, ion beam (cluster ion beam) method, true can be enumerated
Empty vapour deposition method, chemical gaseous phase depositing (CVD, Chemical Vapor Deposition) method etc., with regard to the composition of substrate metal layer
Control etc. is for viewpoint, preferably sputtering method.
When carrying out forming sputtering film to resin film base material, can known sputtering unit carry out film forming, to the resin film of strip
When base material carries out film forming, sputtering unit it can be carried out in a manner of known roller-to-roller.If, can be in length using the roller-to-roller sputtering unit
The surface of the polyimide film of bar, by substrate metal layer and copper film layer continuously film forming.
Fig. 2 is one of roller-to-roller sputtering unit.
Roller-to-roller sputtering unit 10 includes being accommodated with the most rectangular-shape framework 12 of its constituent part.
Framework 12 can be cylindrical shape, but regardless of its shape, can keep being decompressed to 10-4The state of Pa~1Pa scope
.
In in the framework 12, have the polyimide film F's for supplying the resin film substrate as strip to roll out roller 13, tank roller
14th, sputtering cathode 15a, 15b, 15c, 15d, preceding feed rolls 16a, back fed roller 16b, jockey pulley 17a, jockey pulley 17b, takers-in
18。
Rolling out roller 13, tank roller 14, preceding feed rolls 16a, takers-in 18 has power caused by servo motor.Roll out roller 13,
Takers-in 18 keeps polyimide film F equalization of strain by the direct torque of powder coupling etc..
Jockey pulley 17a, 17b are completed for surface by hard chrome plating, and have tension sensor.
Sputtering cathode 15a~15d is configured in opposite directions with magnetron cathode formula with tank roller 14.Sputtering cathode 15a~15d polyamides
The size of imines film F width is wider than polyimide film F width.
Polyimide film F is transported in the roller-to-roller sputtering unit 10 as roller-to-roller vacuum film formation apparatus, in tank
Roller 14 to sputtering cathode 15a~15d film forming, be processed into the polyimide film F2 with copper film layer.
Tank roller 14 is completed for its surface by hard chrome plating, and portion in the inner, from the refrigerant being externally supplied of framework 12
Or warm matchmaker is circulated, approximately fixed temperature is adjusted to.
In using roller-to-roller sputtering unit 10, during by the situation of substrate metal layer and copper film layer film forming, there will be substrate gold
The target for belonging to the composition of layer is installed on sputtering cathode 15a, and copper target is installed on into sputtering cathode 15b~15d, will roll out and set in roller 13
Have after carrying out vacuum exhaust in the device of polyimide film, import the sputter gas such as argon gas, a 1.3Pa left sides will be remained in device
It is right.
In addition, after using sputter by substrate metal layer film forming, also using vapour deposition method, by copper film layer film forming.
(3) copper electrodeposited coating and its film build method
Copper electrodeposited coating is film forming by galvanoplastic.The more satisfactory thickness of the copper electrodeposited coating is 1 μm~20 μm.
Herein, the galvanoplastic used are to use insoluble anode to carry out electricity in the plating bath of the copper sulphate containing iron ion
The method of plating, and the high homogeneity copper sulphate plating of the composition or conventionally used printing distributing board of the copper plating bath used
Apply bath.
Fig. 3 be available for the present invention 2 layers of flexible wiring substrate manufacture roller-to-roller continuous electroplating apparatus (hereinafter referred to as
For plating apparatus 20) one.
It is to roll out roller certainly by the polyimide film F2 with copper film layer obtained by substrate metal layer and copper film layer film forming
22 roll out, and the plating solution 28 being impregnated in repeatedly in electroplating bath 21 on one side continuously transports on one side.Furthermore 28a refers to plating solution
Liquid level.
Polyimide film F2 with copper film layer is during plating solution 28 is impregnated in, by plating in metal foil
The surface of film is by layers of copper film forming, and after the layers of copper of specific thickness is formed, 2 layers of flexible wiring as metallization resin film substrate
With substrate S, batched by takers-in 29.Furthermore the conveyance speed of the polyimide film F2 with copper film layer preferably number m~number
Ten m/ points of scope.
Specifically illustrate, the polyimide film F2 with copper film layer is rolled out into roller 22 certainly rolls out, via power supply roller
26a is impregnated in the plating solution 28 in electroplating bath 21.Into the polyimide film F2 with copper film layer in electroplating bath 21 via
Reverse roll 23 inverts conveyance direction, and is extracted out outside towards electroplating bath 21 by power supply roller 26b.
In this way, it is impregnated in plating solution in the polyimide film F2 with copper film layer to be repeated several times to (being 10 times in Fig. 3)
During, in forming layers of copper on the metallic film of the polyimide film F2 with copper film layer.
Power supply (not shown) is connected between the roller 26a and anode 24a that powers.
Plating circuit is by power supply roller 26a, anode 24a, plating solution, polyimide film F2 and power supply with copper film layer
Form.
In addition, anode is preferably insoluble anode.Insoluble anode need not be particularly limited to, but be coated with conductive ceramic
The known anode on surface.Furthermore in the outside of electroplating bath 21, there is the mechanism that copper ion is supplied to plating solution 28.
Supply of the copper ion to plating solution 28 is to aoxidize copper liquor, the Kocide SD aqueous solution, carbonic acid copper liquor etc.
Supply.Or also have and micro iron ion is added in plating solution, anaerobic copper ball is dissolved, the method for supplying copper ion.Copper
Above-mentioned either method can be used in supply method.
Current density in plating is makes in current density stage with entering conveyance direction downstream from anode 24a
Rise, turn into maximum current density in anode 24o to 24t.
Can be by rising current density in this way, and prevent the discoloration of layers of copper.It is especially relatively thin in the thickness of layers of copper
During situation, the easy discoloration for producing layers of copper if current density is higher, therefore, except the reversion electricity of following periodic reverses
Beyond stream, more satisfactory current density in plating is 0.1A/dm2~8A/dm2.If current density uprises, copper electrodeposited coating is produced
Bad order.
In order to manufacture 2 layers of flexible wiring substrate of the present invention, and in the surface of the thickness with copper electrodeposited coating at a distance of 10%
Scope above is formed using PR electric currents.
When the situation of service life reverse current (hereinafter sometimes referred to PR electric currents), reverse current applies positive current
1~9 times of electric current.
As reverse current time scale, more satisfactory is 1~10% or so.
In addition, the cycle of the reverse current of next flowing of PR electric currents is more satisfactory for the 10m more than second, is more preferably the 20m seconds
~300m the seconds.
Fig. 4 is the figure for the time and current density for schematically showing PR electric currents.
Furthermore plating voltage carries out suitably adjusting in a manner of above-mentioned current density can be achieved.
To be used using 2 layers of flexible wiring of roller-to-roller continuous electroplating apparatus (hereinafter referred to as plating apparatus 20) the manufacture present invention
Substrate, as long as being arised from from the downstream of transport path makes PR electric current flowings in the anode of more than 1, and make PR electric current flowings
Anode quantity by how to set the scope for utilizing PR electric currents to carry out film forming from the surface of copper electrodeposited coating to polyimide film side
Ratio determines.That is, at least anode 24t flowings have a PR electric currents, and make as needed PR electric currents flow into anode 24s, anode 24r,
Anode 24q.
Furthermore PR electric currents can be also flowed into whole anodes, but because the rectifier price of PR electric currents is higher, so system
Cause this increase.Therefore, in 2 layers of flexible wiring substrate of the invention, if using PR electric currents by from the surface of copper electrodeposited coating
10% film forming of thickness on polyimides direction, then before and after the implementation of folding resistance experiment (JIS C-5016-1994), layers of copper
Crystallization orientation ratio [(200)/(117)] difference d [(200)/(111)] can be more than 0.03, therefore, result is can it is expected folding
Property experiment (MIT experiments) lifting.
Expect to be the reason for plating using the copper of PR electric currents, if making current reversal, the crystal grain of the copper of copper electrodeposited coating is straight
Footpath can be that more than 300nm or so, so as to reduce crystal boundary, therefore, can reduce the starting point of caused crackle in crystal boundary.
And then by adding iron ion in copper plating solution, the orientation beyond appearance diffluent (111) is preferentially dissolved,
The crystalline growth of (111) orientation can be made.
The ion of the concentration of iron ion included in copper plating solution, preferably divalent and trivalent adds up to 0.1g~20g/
Rise.
Iron ion, during copper-plated, then cyclically change valence mumber from divalent to trivalent from trivalent to divalent.Then, when
The consumption increase of the ion of iron, uneconomical when the concentration of iron ion rises more than 20g/, moreover, it is diffluent to produce copper coating appearance
Harmful effect.On the other hand, if iron concentration can not expect that the crystallization of (111) orientation is preferentially grown up less than 0.1g/ liters.
In general, in galvanoplastic, the copper that plating separates out is influenceed by through copper-plated substrate surface, if but with PR electricity
Flow more than 10% film forming from the surface of copper electrodeposited coating to thickness, then crystal boundary is can control, therefore, if 2 layers of flexible wiring base
The surface of the copper electrodeposited coating of plate turns into the crystallization for meeting folding resistance to more than the 10% of thickness, then obtains the folding to copper electrodeposited coating
Property effect, so as to may achieve the present invention problem.
Furthermore in what is be adjusted with chemical grinding etc. to the 2 layers of flexible wiring obtained with the thickness of the layers of copper of substrate
During situation, if remain the surface of the layers of copper after self-grind to thickness more than 10% by PR electric current film forming layer, can play
The effect of the present invention.
(4) feature of copper electrodeposited coating
The feature of layers of copper in 2 layers of flexible wiring substrate of the present invention, it is (111) crystallization for the copper for representing more than 1.2
Orientation degree index.In this case, in MIT bend-resistances test (JISC-5016-1994), crystallize and easily slide.Furthermore
In the layers of copper of the flexible wiring substrate of the present invention, in addition to comprising (111) orientation, also match somebody with somebody comprising (200), (220), (311)
To, but wherein (111) orientation accounts for major part, and it crystallizes orientation degree index and is presented more than 1.20.
It is further characterized in that, the orientation ratio of the crystallization before and after MIT folding resistances experiment (JIS C-5016-1994)
The difference of [(200)/(111)] turns into more than 0.03 state.Such a state is regarded as because carrying out the experiment of MIT folding resistances so tying
Crystalline substance slides, so as to cause recrystallization.
For the glossiness on surface, preferably glossy film will be because with avoid that the bumps on surface turn into breach.
In addition, though the size of crystal grain diameter is the bigger the better, also to being matched somebody with somebody flexible wiring with substrate with metal covering etch
Layers of copper etching when line is processed into flexible wiring impacts, therefore it must be noted that.
When the situation of ferric chloride in aqueous solution is used in the etching of the layers of copper in metal covering etch, there is also the crystalline substance of layers of copper
Grain diameter situation about not impacting, but in etched copper crystalline particle crystal boundary situation when, crystal grain diameter is also to distribution
Shape impact.It is more satisfactory for 200nm~400nm or so as crystal grain diameter.If below 200nm, then crystal boundary compared with
It is more, the crackle as break origins is easily produced, and it is the flatness for keeping metal surface the reason for be set to below 400nm.
Moreover, the layers of copper of flexible wiring substrate of the present invention obtains by the film build method of above-mentioned layers of copper, from into
The characteristic and crystal grain for being more than 0.03 for the difference with the front and rear crystallization orientation ratio [(200)/(111)] of MIT bend-resistances experiment are straight
Footpath is the layers of copper of more than 300nm characteristic etc..In addition, the crystallization orientation of copper electrodeposited coating and crystal grain diameter can fill according to X-raydiffraction
Put and know.
And then the copper crystallization of the layers of copper of method described above acquisition is that have the dynamic recrystallization effect under normal temperature when bending
Should.Average crystal grain diameter after folding resistance experiment has the tendency for turning into 100nm~200nm or so because of recrystallization.
It is generally believed that the electroplating film of copper does not produce dynamic recrystallization under normal temperature.However, the flexible wiring base of the present invention
Plate produces dynamic recrystallization under normal temperature, therefore, as a result, being difficult to cut off if carrying out the sample if the cripping test of MIT experiments.
Dynamic recrystallization under the average crystallite particle diameter and normal temperature of layers of copper can be by profile scanning ion microscope (SIM (Scanning
Ion Microscope)) as being observed.
Secondly, more satisfactory arithmetic surface roughness Ra is less than 0.2 μm.
If surface roughness Ra more than 0.2 μm, even if crystallization orientation ratio that the experiment of MIT folding resistances is front and rear [(200)/
(111) difference] is more than 0.03, and the improvement of folding resistance is also less.Therefore, it is more satisfactory to be, before and after the experiment of MIT folding resistances
The difference for crystallizing orientation ratio [(200)/(111)] is more than 0.03, and arithmetic surface roughness Ra is less than 0.2 μm.
Certainly, when the situation being ground with chemical grinding etc. to the surface of layers of copper, the table of the layers of copper after chemical grinding
The arithmetic surface roughness Ra in face is less than 0.2 μm.
(5) flexible wiring
The flexible wiring of the present invention is to carry out distribution with substrate to 2 layers of flexible wiring of the present invention with metal covering etch
Process and manufacture.
The etching solution that copper electrodeposited coating etc. used in the etching and processing of distribution processing is not limited to special allotment
The aqueous solution comprising iron chloride, copper chloride and copper sulphate or special decoction, it can be used and common include proportion 1.30~1.45
Ferric chloride in aqueous solution or proportion 1.30~1.45 copper chloride solution commercially available etching solution.
In the surface of distribution, implement tin plating, nickel plating, gold-plated etc. in necessary position as needed, and with known welding resistance
Agent etc. covers surface.Then, the electronic components such as semiconductor subassembly are installed, form electronic installation.
Embodiment
Hereinafter, the present invention is further illustrated using embodiment.
Polyimide film with copper film layer is to be manufactured using roller-to-roller sputtering unit 10.
By the weight % evanohm targets of nickel -20 of substrate metal layer film forming are installed on into sputtering cathode 15a, copper target is installed
In sputtering cathode 15b~15d, and it is provided with polyimide film (Kapton, registration mark, the TORAY-DUPONT of 38 μm of thickness
Company manufactures) device in carry out vacuum exhaust after, import argon gas, will remain 1.3Pa in device, manufacture has copper film layer
Polyimide film.The thickness of substrate metal layer (nichrome) is 20nm, and the thickness of copper film layer is 200nm.
To the polyimide film with copper film layer of gained, copper plating is carried out using plating apparatus 20, by copper electrodeposited coating
Film forming.Plating solution then turns into maximum electricity unless otherwise noted using the copper sulfate solution that pH is less than 1, anode 24o to 24t
Current density (except the reverse current of PR electric currents), and to adjust electric current close in a manner of the thickness of final copper electrodeposited coating turns into 8.5 μm
Degree.
Folding resistance experiment is that iron chloride is used for into etching solution, and JIS-C-5016-1994 survey is formed with metal covering etch
Attempt case, and evaluated according to identical standard.
The crystallization orientation of the front and rear copper electrodeposited coating of folding resistance experiment is that Wilson orientation degree index is used in X-raydiffraction
It is measured.
Embodiment 1
In order to be electroplated in the film thickness range from the surface of copper electrodeposited coating to 10% using PR electric currents, and make PR electric current streams
Enter anode 24t, make 2 layers of flexible wiring substrate of embodiment 1.It is 5g/ liters to make iron concentration.
(111) crystallization orientation degree index of copper electrodeposited coating before the experiment of MIT folding resistances is before 1.34, MIT folding resistances are tested
The difference of the crystallization orientation ratio [(200)/(111)] of x-ray orientation degree exponential representation afterwards is 0.04, crystal grain diameter 383nm, arithmetic table
Surface roughness Ra is the sample of 0.06 μm of embodiment 1, and the good result of 349 times is obtained in the experiment of MIT folding resistances.
Embodiment 2
MIT folding resistances experiment before copper electrodeposited coating crystallization orientation be (111) crystallize orientation degree index be 1.36, in order to
Electroplated from the film thickness range on the surface of copper electrodeposited coating to 40% using PR electric currents, and make PR electric currents flow into anode 24r~
24t, in addition, carry out similarly to Example 1, make 2 layers of flexible wiring substrate of embodiment 2.
The difference of the crystallization orientation ratio [(200)/(111)] of the front and rear x-ray orientation degree exponential representation of MIT folding resistances experiment is
0.05th, crystal grain diameter 363nm, the sample for the embodiment 2 that arithmetic surface roughness Ra is 0.18 μm, in the experiment of MIT folding resistances
Obtain the good result of 247 times.
Embodiment 3
The crystallization orientation of copper electrodeposited coating before the experiment of MlT folding resistances is that (111) crystallization orientation degree index is 1.37, in order to
Film thickness range on the surface from copper electrodeposited coating to 40% is electroplated using PR electric currents, and make PR electric currents flow into anode 24r~
24t, it is 0.1g/ liters to make iron concentration, in addition, is carried out similarly to Example 1, and 2 layers of flexibility for making embodiment 3 are matched somebody with somebody
Line substrate.
The difference of the crystallization orientation ratio [(200)/(111)] of the front and rear x-ray orientation degree exponential representation of MIT folding resistances experiment is
0.05th, crystal grain diameter 327nm, the sample for the embodiment 3 that arithmetic surface roughness Ra is 0.20 μm, in the experiment of MIT folding resistances
Obtain the result of 180 times.
(comparative example 1)
MIT folding resistances experiment before copper electrodeposited coating crystallization orientation be (111) crystallize orientation degree index be 0.98, in order to
Electroplated from the film thickness range on the surface of copper electrodeposited coating to 8% using PR electric currents, and PR electric currents is flowed into anode 24t, make it
The current density of anode is the 80% of embodiment 1, in addition, is carried out similarly to Example 1,2 layers of comparison example 1 are scratched
Property distribution substrate.
The difference of the crystallization orientation ratio [(200)/(111)] of the front and rear x-ray orientation degree exponential representation of MIT folding resistances experiment is
0.02nd, crystal grain diameter 280nm, the sample for the comparative example 1 that arithmetic surface roughness Ra is 0.15 μm, in the experiment of MIT folding resistances
Obtain the result that improvement is not presented of 135 times.
(comparative example 2)
MIT folding resistances experiment before copper electrodeposited coating crystallization orientation be (111) crystallize orientation degree index be 0.85, in order to
Electroplated from the film thickness range on the surface of copper electrodeposited coating to 5% using PR electric currents, and PR electric currents is flowed into anode 24t, make it
The current density of anode is the 50% of embodiment 1, in addition, is carried out similarly to Example 1,2 layers of comparison example 2 are scratched
Property distribution substrate.
The difference of the crystallization orientation ratio [(200)/(111)] of the front and rear x-ray orientation degree exponential representation of MIT folding resistances experiment is
0.01st, crystal grain diameter 195nm, the sample for the comparative example 2 that arithmetic surface roughness Ra is 0.16 μm, in the experiment of MIT folding resistances
Obtain the result that improvement is not presented of 83 times.
(comparative example 3)
MIT folding resistances experiment before copper electrodeposited coating crystallization orientation be (111) crystallize orientation degree index be 1.06, in order to
Electroplated from the film thickness range on the surface of copper electrodeposited coating to 9% using PR electric currents, and PR electric currents is flowed into anode 24t, make it
The current density of anode is the 90% of embodiment 1, in addition, is carried out similarly to Example 1,2 layers of comparison example 3 are scratched
Property distribution substrate.
The difference of the crystallization orientation ratio [(200)/(111)] of the front and rear x-ray orientation degree exponential representation of MIT folding resistances experiment is
0.02nd, crystal grain diameter 190nm, the sample for the comparative example 3 that arithmetic surface roughness Ra is 0.11 μm, in the experiment of MIT folding resistances
Obtain the result that improvement is not presented of 141 times.
Description of reference numerals
1 polyimide film (resin film substrate)
2 substrate metal layers
3 copper film layers
4 bronze medal electrodeposited coatings
5 layers of copper
62 layers of flexible wiring substrate
10 roller-to-roller sputtering units
12 frameworks
13 roll out roller
14 tank rollers
15a, 15b, 15c, 15d sputtering cathode
Feed rolls before 16a
The back fed rollers of 16b
17a, 17b jockey pulley
18 takers-ins
The continuous plating apparatus of 20 roller-to-roller modes
21 electroplating baths
22 roll out roller
23 reverse rolls
24a~24t anodes
26a~26k power supply rollers
28 plating solutions
The liquid level of 28a plating solutions
29 takers-ins
F resin film substrates (polyimide film)
Polyimide films (the tree film substrate that carries copper film layer) of the F2 with copper film layer
2 layers of flexible wiring substrates of S
Claims (5)
1. a kind of 2 layers of flexible wiring substrate, 2 layers of flexible wiring substrate, for provided with not by bonding agent and in polyamides
Substrate metal layer that the surface of imines film is made up of nickel alloy and the layers of copper that is set on the surface of the substrate metal layer it is laminated
2 layers of flexible wiring substrate of structure, it is characterised in that：
The crystallization orientation ratio of the layers of copper obtained before and after the implementation that the folding resistance as defined in JIS C-5016-1994 is tested
The difference d [(200)/(111)] of [(200)/(111)] is more than 0.03, and the crystallization orientation degree index in (111) face of the layers of copper is
More than 1.2, crystal grain diameter is more than 300nm, and then,
Copper film layer of the layers of copper by the surface filming in the substrate metal layer and the surface filming in the copper film layer
Copper electrodeposited coating form,
The copper electrodeposited coating, from its surface in more than the 10% of thickness thickness range, by short based on periodically carrying out
The copper of the periodic reverse of the current potential upset of time is electroplated to be formed,
The copper plating, adds iron ion in copper plating solution and carries out.
2. 2 layers of flexible wiring substrate as claimed in claim 1, it is characterised in that the thickness of the layers of copper is 5 μm~12 μ
m。
3. 2 layers of flexible wiring substrate as claimed in claim 1 or 2, it is characterised in that the surface roughness of the layers of copper,
It it is less than 0.2 μm by arithmetic average roughness Ra.
4. a kind of flexible wiring, the flexible wiring is provided with the distribution of laminate structures, and the distribution of the laminate structures possesses
The substrate metal layer and the table in the substrate metal layer that the surface of polyimide film is not formed by bonding agent and by nickel alloy
The layers of copper in face, it is characterised in that：
The crystallization orientation ratio of the layers of copper obtained before and after the implementation that the folding resistance as defined in JIS C-5016-1994 is tested
The difference d [(200)/(111)] of [(200)/(111)] is more than 0.03, and the crystallization orientation degree index in (111) face of the layers of copper is
More than 1.2 and crystal grain diameter be more than 300nm, and then,
Copper film layer of the layers of copper by the surface filming in the substrate metal layer and the surface filming in the copper film layer
Copper electrodeposited coating form,
The copper electrodeposited coating, from its surface in more than the 10% of thickness thickness range, by short based on periodically carrying out
The copper of the periodic reverse of the current potential upset of time is electroplated to be formed,
The copper plating, adds iron ion in copper plating solution and carries out.
5. flexible wiring as claimed in claim 4, it is characterised in that the surface roughness of the layers of copper, by arithmetic average
Roughness Ra is less than 0.2 μm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-219366 | 2013-10-22 | ||
| JP2013219366 | 2013-10-22 |
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| JP (1) | JP6398596B2 (en) |
| KR (1) | KR101626214B1 (en) |
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| KR102525201B1 (en) | 2016-03-22 | 2023-04-25 | 삼성디스플레이 주식회사 | Flexible electronic device |
| JP6667728B2 (en) * | 2018-03-23 | 2020-03-18 | 古河電気工業株式会社 | Lead frame material, method of manufacturing the same, and semiconductor package using the same |
| JP7087759B2 (en) * | 2018-07-18 | 2022-06-21 | 住友金属鉱山株式会社 | Copper-clad laminate |
| KR102364447B1 (en) * | 2020-07-20 | 2022-02-17 | 도레이첨단소재 주식회사 | Flexible copper clad laminate film, and electronic device including the same |
| WO2022176094A1 (en) * | 2021-02-18 | 2022-08-25 | Tdk株式会社 | Layered resin film, collector, and secondary battery |
| CN113113973B (en) * | 2021-04-19 | 2023-01-03 | 重庆触视科技有限公司 | Wireless quick charging design method and device |
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| JP3563730B2 (en) * | 2002-06-07 | 2004-09-08 | 松下電器産業株式会社 | Flexible printed circuit board |
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| TW201109468A (en) * | 2009-07-03 | 2011-03-16 | Mitsui Mining & Smelting Co | Flexible copper covered laminate board, flexible printed circuit board for chip-on-film, and method for making same |
| TW201338647A (en) * | 2011-11-22 | 2013-09-16 | Panasonic Corp | Flexible metal clad substrate, method for manufacturing flexible metal clad substrate, printed wiring board, multilayer flexible printed wiring board, and flex-rigid printed wiring board |
| CN104247576A (en) * | 2012-04-24 | 2014-12-24 | 住友金属矿山株式会社 | Two-layered flexible wiring substrate, flexible wiring board, and methods for producing same |
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| CN104582257A (en) | 2015-04-29 |
| JP2015108187A (en) | 2015-06-11 |
| KR101626214B1 (en) | 2016-05-31 |
| TW201528232A (en) | 2015-07-16 |
| KR20150046751A (en) | 2015-04-30 |
| JP6398596B2 (en) | 2018-10-03 |
| TWI540549B (en) | 2016-07-01 |
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