CN102792786B

CN102792786B - 2 layers of flexible substrate and manufacture method thereof

Info

Publication number: CN102792786B
Application number: CN201180013870.7A
Authority: CN
Inventors: 西村英一郎; 浅川吉幸
Original assignee: Sumitomo Metal Mining Co Ltd
Current assignee: Sumitomo Metal Mining Co Ltd
Priority date: 2010-03-16
Filing date: 2011-03-10
Publication date: 2015-11-25
Anticipated expiration: 2031-03-10
Also published as: TWI510673B; CN102792786A; KR101363771B1; JP5672299B2; KR20120127743A; WO2011114997A1; TW201139730A; JPWO2011114997A1

Abstract

The invention provides 2 layers of flexible substrate and manufacture method thereof, the Copper Foil rete that described 2 layers of flexible substrate do not have the pin hole because producing when utilizing the process of dry type plating to form substrate metal layer in insulator film and cause and layers of copper defect, the defect of substrate metal layer is few, and the adaptation of insulator film and substrate metal layer, corrosion resistance, resistance to water are all excellent, be particularly applicable to 2 layers of flexible substrate that fine pattern is formed, COF installs.2 layers of flexible substrate of the present invention are at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, this substrate metal layer utilize dry type plating form 2 layers of flexible substrate of copper film layer and/or layers of copper, wherein, above-mentioned insulator film is that the oligomer amount of the above-mentioned insulator film after surface treatment is less than 70% of the oligomer amount of the insulator film before surface treatment through implementing surface treatment.

Description

2 layers of flexible substrate and manufacture method thereof

[technical field]

The invention relates to 2 layers of flexible substrate and manufacture method thereof, more specifically, in insulator film, form substrate metal layer (below sometimes also claim " Seed Layer ") according to dry type plating about working as, when then forming layers of copper again, pin hole and the few 2 layers of flexible substrate of concave defect and manufacture method thereof.

[background technology]

Now slim, small-sized, lightweight is required to LCD, mobile phone, digital camera and various electronic instruments etc., electronic component carried thereon has the trend towards miniaturization, and has for forming the substrate of electronic circuit: " the rigidity printing distributing board " of hard board and film-form and tool flexibility also can " flexible printed wiring board (also claiming " FPC ") " of free bend below sometimes.

Particularly FPC utilizes its flexibility, can be used in such as: the hinge part of lcd driver distributing board, HDD (hard disk drive), DVD (biometrics multifunctional optical disk) module, mobile phone requires the place of tortuosity like that, and thus this demand will increase day by day.

As this FPC materials'use is on the insulation film such as polyimides, polyester, pastes the copper-surfaced laminated plate (sometimes also claiming " CCL " below) of Copper Foil (conductor layer).

This CCL rough classification has 2 kinds.The CCL that first insulation film and Copper Foil (conductor layer) utilize bonding agent to carry out pasting (claims " 3 layers of CCL " usually, hereinafter referred to as " 3 layers of CCL "), another is that insulation film and Copper Foil (conductor layer) be not when using bonding agent, casting method, layered manner, metallization etc. is utilized directly to carry out the CCL (usually claiming " 2 layers of CCL ", hereinafter referred to as " 2 layers of CCL ") of compound.

If should " 3 layers of CCL " compare with " 2 layers of CCL ", with regard to manufacturing cost, because 3 layers of CCL are easy, thus cheap at the manufacture view such as fee of material, operability of insulation film, bonding agent etc.On the other hand, with regard to the characteristics such as thermal endurance, filming, dimensional stability, be then 2 layers of CCL excellence, by the fine patterning of circuit, the impact of high-density installation, though belong to high unit price, can 2 layers of CCL demand of slimming expand gradually.

Moreover the method for installing IC on FPC is with after form Wiring pattern on CCL, the COF that the light recycled through insulator film detects IC position is installed as main flow, and requires the thinness of material itself and the transparency of insulating material.Put also is that 2 layers of CCL are favourable at this point.

There is the manufacture method of 2 layers of CCL of such feature, roughly can be categorized as 3 kinds.1st kind is the method utilizing casting method to paste insulation film on electrolytic copper foil or rolled copper foil.2nd kind is the method utilizing layered manner to paste electrolytic copper foil or rolled copper foil on insulation film.The third is on insulation film, utilize dry type plating (so-called " dry type plating " refers to sputtering method, ion plating method, cluster ions bundle (clusterionbeam) method, vacuum vapour deposition, CVD etc.) herein, insulation film arranges the substrate metal layer of film, then face is carried out electro-coppering and forms the method for layers of copper thereon.Usually the third method is called " metallization ".

Because this metallization is by using dry type plating and wet type plating (such as electroplating), and freely can control this metal layer thickness, thus with regard to the filming of metal level, be in a ratio of easily with casting method or layered manner.Further, because the flatness at polyimides and metal level interface is high, thus it is generally acknowledged and be applicable to fine pattern.

But, utilize the CCL that metallization obtains, because metal-insulator film interface is level and smooth, the anchoring effect that bonding thus between metal with insulation film cannot expecting generally utilizes, and the problem that the dhering strength having interface cannot fully manifest.

Namely, the 2 layers of CCL using this metallization to be formed, if be implemented in 121 DEG C, 95%RH, 2 atmospheric high temperature, high humidity, long-time " PCT test (PressureCookerTest; high-pressure water gas is tested) " placed under high pressure, compared with initial stage dhering strength, there will be the tendency that dhering strength significantly reduces.Thus, if consider in pattern forming step liquid resist coating after dry time, the heat of about 100 ~ 150 DEG C can be applied in, and when the joint installed on formed pattern when IC etc. and the heat that also can apply about 250 DEG C when welding, and utilize the sealing resins such as solder resist to carry out sealing etc. item the distribution that pattern is formed, known fine pattern according to layer CCL of 2 manufactured by metallization and under not being suitable for high temperature is formed, COF installs, and causes thermal endurance, the lifting of moisture-proof necessitates and obligato problem.

As the solution for problem like this, it is that such as patent documentation 1 motion has: the method forming the intermediate layer (Seed Layer) using Ni, Cr metal alloy layer that is principal component as insulation film and layers of copper, but when formed more fine pattern time, just must more improve its moisture-proof.

Moreover, patent documentation 2 records following method: directly have at least one side of plastic film substrate by copper or with copper form by the alloy of principal component Copper thin film flexible printed wiring board among, this Copper thin film holds: the superficial layer with crystalline texture, and between this superficial layer and plastic film substrate, be provided with 2 Rotating fields of bottom surface layer of polycrystalline structure, and the X ray of Copper thin film is resolved in pattern, the peak intensity of lattice plane index (200) is less than 0.1 divided by value X ray relative intensity ratio (200)/(111) of the peak intensity of lattice plane index (111), and bottom surface layer utilizes use the plasma treatment of nitrogenous mist and generate functional group on plastic film substrate, and formation is the metal that the alloy of principal component is formed by copper or with copper, carry out chemical bonding by this metal with the atom forming plastic film substrate and form, thus lifting moisture-proof.But, this invention be rely on the control of lattice plane, with the composite effect to be produced by plasma treatment and reaching, but it is difficult technically to control this lattice plane, is difficult to stably produce in a large number.

But; for substrate metal layer film forming in insulator film; generally use vacuum vapour deposition, sputtering method, ion plating method etc.; but because the pin hole that usually can be produced multiple tens of μm ~ hundreds of μm of sizes by rete obtained according to this dry type plating, thus often there is the insulator film exposed portion because this pin hole causes in substrate metal layer.

At present, in this flexible wiring, the thickness of the copper conductive cell envelope required for distribution is above 35 μm and is appropriate to 50 μm, but because the width that institute forms distribution also has about hundreds of μm, so seldom wiring part generation defect can be caused because of the existence of ten μm of pin holes.

But, when for obtain target of the present invention there is the narrow flexible wiring with the wiring part of thin space time, as aforementioned, the very narrow thickness that the thickness being preferred for the copper tunicle that wiring part is formed is less than 15 μm, more preferably less than 8 μm, ideal is about 5 μm, the possibility causing wiring part to produce defect improves.

If for this situation, with be used in be formed with substrate metal layer insulator film on form the 2 layer flexible substrate of copper by rete of desired thickness, it is that example is described that utilization removes the situation that method (subtractivemethod) carries out flexible wiring manufacture, then the formation of wiring part pattern implements according to following step.

(1) resist layer of wiring part pattern needed for the copper conductor layer having and only cover wiring part but expose non-wiring part is set on copper conductor layer.

(2) chemical etching process implemented to the copper conductor layer exposed and remove.

(3) finally resist layer is peeled off removing.

Therefore, when use be formed such as 5 μm of very thin copper by the substrate of thicknesses of layers, Production Example is as wide in distribution 15 μm, wiring closet is wide apart from the narrow distribution of 30 μm, during the distributing board of narrow wiring closet distance, in the pin hole produced on the substrate metal layer of substrate because of the process of dry type plating, thick large young pathbreaker reaches tens of μm to hundreds of μm grades, thus when the electro-coppering tunicle of formation 5 μm of left and right thicknesses, the insulator film exposed portion of causing because of pin hole almost cannot be buried, so this exposed portion (i.e. the defect part of conductor layer) can involve wiring part, wiring part is caused to occur defect in pin hole position and become distribution defect, both made not also can become like this to cause the closely sealed bad reason of wiring part.

Therefore, patent documentation 3 discloses: the technology of the pinhole number of regulation metal salt/polyimide thin-film laminate.But patent documentation 3 pin hole of non-public vapor-deposited film, but the pin hole after regulation electro-coppering, the pin hole about vapor-deposited film and substrate metal layer there is no any mentioning.

Moreover, as solution to the problems described above, patent documentation 4 records: in insulator film, utilize dry type plating to form substrate metal layer, and then bestow and utilize the copper coating of non-electrolytic plating as intermediate metal layer, by method coating for the insulator film exposed portion of causing because of pin hole.

But, though the method can eliminate the insulator film exposed portion because pin hole causes really to a certain degree, but then, the plating solution used when having learnt electroless plating Copper treatment and its pretreatment fluid etc., can from established size pin hole partial penetration miscellaneous between insulator film and substrate metal layer, this likely can become the adaptation of substrate metal layer and utilize institute to form the reason of the conductor layer adaptation formation obstruction caused by electro-coppering afterwards, and non-sufficient solve scheme.Further, even if utilize electro-coppering can buried insulation body thin film exposed portion, but because the closing force between insulation film and layers of copper is low, if thus substrate metal layer has pin hole, just can becomes and cause the closely sealed bad reason reduced with insulating reliability.

[prior art document]

[patent documentation]

Patent documentation 1: Japanese Patent Laid-Open 2006-13152 publication

Patent documentation 2: No. 3563730th, Japan Patent

Patent documentation 3: Japanese Patent Laid-Open 11-92917 publication

Patent documentation 4: No. 10-195668, Japanese Patent Laid-Open

[summary of the invention]

Invent problem to be solved

The object of the invention is to solve the problems referred to above when using 2 layers of flexible substrate of dry type plating to manufacture, and provide: do not have the defect causing Copper Foil rete and layers of copper because of the pin hole that produces when utilizing the process of dry type plating to form substrate metal layer in insulator film, the defect of substrate metal layer is few, and 2 layers of flexible substrate that the adaptation of insulator film and substrate metal layer, corrosion resistance, resistance to water are all excellent, particularly be applicable to 2 layers of flexible substrate that fine pattern is formed, COF installs, and manufacture method.

For the means of dealing with problems

The present inventor etc. find by being used at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, and on this substrate metal layer, form the required copper film layer of thickness and/or 2 layers of flexible substrate of layers of copper, wherein, this insulator film is through implementing surface-treated, and oligomer amount is 2 layers of flexible substrate of less than 70% of oligomer amount before surface treatment, just the defect not having and cause copper film layer and layers of copper because of the pin hole that produces when forming substrate metal layer can be obtained, and the defect of substrate metal layer is also few, and the adaptation of insulator film and base metal interlayer, corrosion resistance, and 2 layers of flexible substrate that resistance to water is all excellent, also be applicable to have narrow, the flexible wiring of the wiring part of thin space, thus complete the present invention.

The present invention the 1st invention is 2 layers of flexible substrate, it is at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, this substrate metal layer utilizes dry type plating form 2 layers of flexible substrate of copper film layer, wherein, insulator film is at least simultaneously implementing surface treatment, only implementing the oligomer amount after this surface treatment to the one side of insulator film, is less than 70% of the oligomer amount before surface treatment.

The present invention the 2nd invention is the thickness that the copper film layer of the 1st invention has 50nm ~ 500nm, and does not have the pin hole of diameter more than 30 μm, and diameter more than 5 μm and the pin hole of less than 30 μm is every 1 square metre less than 45000.

The present invention the 3rd invention is 2 layers of flexible substrate of the 1st and the 2nd invention, wherein, copper film layer utilizes wet type plating form copper wet type plating layer.

The present invention the 4th invention is that the copper wet type plating layer of the 3rd invention has 0.5 μm ~ 12 μm thickness, and there is no the long concave defect more than 20 μm of diameter or greatest drawback, and diameter or greatest drawback long more than 10 μm and the concave defect of less than 20 μm is every 1 square metre less than 2200.

The present invention the 5th invention is 2 layers of flexible substrate of the 1st to the 4th invention, wherein, substrate metal layer has 5nm ~ 50nm thickness, formed by containing nickel-chromium alloy, described nickel-chromium alloy be Addition ofelements 6 % by weight ~ 22 % by weight surplus based on chromium then by nickel is formed, and the thickness of the conductor layer (layers of copper) be made up of copper film layer and copper wet type plating layer set on substrate metal layer is 50nm ~ 12 μm.

The present invention the 6th invention is the insulator film of the 1st to the 5th invention is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

The present invention the 7th invention is the surface treatment of the 1st to the 6th invention is implement to the surface of insulator film the plasma discharge process utilizing 1500V ~ 3000V direct voltage under the inert environments of pressure 0.8Pa ~ 4.0Pa.

The present invention the 8th invention is the surface-treated inert environments of the 7th invention is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

The present invention the 9th invention is the surface treatment of the 1st to the 6th invention is under the inert environments of pressure 0.8Pa ~ 4.0Pa, implements to the surface of insulator film the plasma discharge process utilizing 800V ~ 2000V high frequency voltage.

The present invention the 10th invention is the surface-treated inert environments of the 9th invention is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

The present invention the 11st invention is at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, above-mentioned substrate metal layer utilize dry type plating form the manufacture method of 2 layers of flexible substrate of copper film layer, wherein, to the surface of this insulator film under the inert environments of pressure 0.8Pa ~ 4.0Pa, execution forms substrate metal layer after utilizing and applying the surface treatment of the plasma discharge in 2 ~ 100 seconds between the pairing sparking electrode of plasma electrode.

The present invention the 12nd invention is the surface treatment utilizing plasma discharge of the 11st invention, be plasma electrode sparking electrode between apply 1500V ~ 3000V direct voltage.

The present invention the 13rd invention is the surface treatment utilizing plasma discharge of the 11st invention, be plasma electrode sparking electrode between apply 800V ~ 2000V high frequency voltage.

The present invention the 14th invention is the manufacture method of 2 layers of flexible substrate of the 8th invention, on at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, this substrate metal layer utilize dry type plating form copper film layer, wherein, to the surface of insulator film under the nitrogen environment of pressure 0.8Pa ~ 4.0Pa, implement to utilize and apply 1500V ~ 3000V direct voltage 2 ~ 100 second between the pairing sparking electrode of plasma electrode and after the surface treatment of plasma that produces, form substrate metal layer.

The present invention the 15th invention is the manufacture method of 2 layers of flexible substrate of the 10th invention, on at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, this substrate metal layer utilize dry type plating form copper film layer, wherein, to the surface of insulator film under the nitrogen environment of pressure 0.8Pa ~ 4.0Pa, implement to utilize and apply 800V ~ 2000V high frequency voltage 2 ~ 100 second between the pairing sparking electrode of plasma electrode and after the surface treatment of plasma that produces, form substrate metal layer.

The present invention the 16th invention to be the dry type plating of the 11st to the 15th invention be in vacuum vapour deposition, sputtering method and ion plating method any one.

The present invention the 17th invention is the insulator film of the 11st to the 16th invention is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

(invention effect)

According to the present invention, the copper film layer and copper wet type plating layer defect that do not have because the pin hole that produces when forming substrate metal layer causes can be obtained, the defect of substrate metal layer is also few, and the adaptation of insulator film and substrate metal layer and the equal 2 layers of excellent flexible substrate of corrosion resistance.These 2 layers of flexible substrates are also applicable to have flexible wiring that is narrow, thin space wiring part, thus play industrially significant effect.

[embodiment]

1.2 layers of flexible substrate

2 layers of flexible substrate of the present invention are at least one side of insulator film; in not via bonding agent when; dry type plating is utilized to be provided with substrate metal layer; and on this substrate metal layer, be provided with the structure of copper film layer; it is characterized in that: this insulator film is by implementing surface treatment, and makes oligomer amount become the oligomer amount of less than 70% of the oligomer amount before surface treatment; By implementing surface treatment to insulator film, compared with the oligomer amount before surface treatment, making the surface of the oligomer amount becoming less than 70%, just can suppress the generation of thick pin hole.

Moreover 2 layers of flexible substrate of the present invention preferably have the copper film layer of thickness 50nm ~ 500nm, and there is no the pin hole of diameter 30 μm, and the pin hole of diameter 5 μm to 30 μm is less than 45000 at every 1 square metre.

1-1. copper film layer

Preferred 50nm ~ the 500nm of thickness of copper film layer.

If the thickness of this Copper Foil rete is less than 50nm, when utilizing the follow-up electrocoppering as one of wet type plating to implement the film forming of copper wet type plating layer on the surface at copper film layer, the resistance value of copper film layer can improve, and can make the plating appearance degradation on layers of copper surface.In addition, when utilizing electrocoppering to carry out the film forming of copper wet type plating layer, copper film layer plays function as negative electrode, and the resistance value of copper film layer just can become problem.On the other hand, if the thickness of copper film layer carries out film forming more than 500nm, though the pin hole then between Copper thin film has minimizing, this is utilizing dry type plating by consuming time for copper film layer film forming, less economical.

Generally speaking, copper film layer and copper wet type plating layer are thicker, and the copper of institute's film forming more can be grown up and bury pin hole, and thus pin hole is little, even can tail off.So compared with dry type plating, the wet type plating utilizing film forming speed fast arranges copper wet type plating layer on the surface at copper film layer, and manufactures 2 layers of flexible substrate.These 2 layers of flexible substrates utilize wet type plating to make the pinhole number on its surface become small.But even if the pin hole on 2 layers of flexible substrate surface is buried, but the pin hole of substrate metal layer and copper film layer is in not buried state.

So, if when not suppressing aperture size and the quantity of substrate metal layer and copper film layer, form the wiring part pattern of narrow wiring closet distance, wiring part conveniently can expose without the ground of substrate metal layer, cause becoming distribution defect, also can become even if really not so and cause the closely sealed bad reason of wiring part.

Moreover, though the pin hole of copper film layer utilizes wet type plating and buried, if there is the pin hole of copper film layer, then substrate metal layer just can be exposed in air before wet type plating, thus substrate metal layer just can go bad, and causing becomes distribution defect and the closely sealed bad reason of wiring part.

Thus, in copper film layer of the present invention, even if having pin hole, the pin hole of to be also size be diameter 5 μm ~ 30 μm is preferably in the scope of less than 45000 at every 1 square metre.Thus and unspecified quantity in addition, the pin hole of diameter less than 5 μm because cause distribution defect, closely sealed bad situation few, and detects also difficulty.

By using above-mentioned formation, just can obtain not have causes copper by the defect of membranous part because of the pin hole that produces when forming substrate metal layer, and the defect of substrate metal layer is few, and 2 layers of flexible substrate that the adaptation of insulator film and substrate metal layer, corrosion resistance and resistance to water are all excellent.

The surface treatment of 1-2. insulator film (base material)

To the surface treatment of the insulator film of base material, be use plasma treatment to implement.Surface treatment can implement the one side of insulator film, but have more effect to two-sided enforcement.

Treatment conditions are under inert environments, the pressure of 0.8Pa ~ 4.0Pa.Under the inert environments of insufficient pressure 0.8Pa, plasma discharge not easily in stable, if under the inert environments surmounting pressure 4.0Pa, because process can become by force, causes insulation film to occur wrinkling situation when thus having process, therefore not preferred.

Between the pairing sparking electrode of plasma electrode, apply the direct voltage of 1500V ~ 3000V, and implement direct-current plasma (DC plasma) process.If this direct voltage is less than 1500V, the process then utilizing plasma to implement is excessively weak, the rising of initial stage dhering strength cannot be shown, if more than 3000V, then because process can become strong, thus easily cause insulation film to occur during process wrinkling with distortion, cause the result that heat-resisting dhering strength and PCT peel strength are reduced on the contrary, thus not preferred.

Between the pairing sparking electrode of plasma electrode, apply the high frequency voltage of 800V ~ 2000V, and implement high-frequency plasma (RF plasma) process.If this high frequency voltage is less than 800V, then the process utilizing plasma to implement is excessively weak, cannot show the rising of initial stage dhering strength, if more than 2000V, then because process can become by force, thus during process, easily cause insulation film appearance wrinkling with distortion, thus not preferred.

In addition, so-called " under inert environments " refers to the 18th race's gas such as nitrogen, argon herein, also can be the mist of nitrogen and argon.If particularly utilize plasma to implement surface treatment under nitrogen environment, PCT peel strength just can be made to become more than 70% of initial stage peel strength.

Preferably 2 seconds ~ 100 seconds processing time utilizing plasma discharge to implement.If the processing time of plasma discharge was less than 2 seconds, then processed weak, cause the rising not tool contribution to initial stage dhering strength, process is implemented if continued more than 100 seconds, then impact can be excessive, cause insulation film easily to occur wrinkling with distortion, instead can cause the result that heat-resisting dhering strength and PCT dhering strength reduce, thus not preferred.On the other hand, from productive viewpoint, the long process time more than 100 seconds is not preferred yet.

The insulator film of base material is that oligomer amount is more, then the pin hole of copper film layer more increases.

When implementing surface treatment to the one side of insulator film, the oligomer amount of the insulator film after surface treatment, the oligomer amount before surface treatment of comparing is compared, preferably below 70%.Further, when two-sided execution surface treatment to insulator film, the oligomer amount of the insulator film after surface treatment, compared with the oligomer amount before surface treatment, is preferably less than 35%.

The reason utilizing this surface treatment to cause oligomer amount to reduce is caused by the oligomer cause that can be removed because of surface treatment.Herein, so-called " oligomer " is the molecule of molecular weight 300 ~ 14000 scope, when when manufacturing insulator film, does not fully carry out being polymerized and residuing in the molecule in film.The judgement of this oligomer amount is tried to achieve according to as following mensuration oligomer amount.From insulator film, use oxolane equal solvent to extract oligomer, then use size exclusion chromatography method (SEC method) determining molecular weight to distribute this extract.

1-3. substrate metal layer

Preferred 5nm ~ the 50nm of thickness of substrate metal layer.

If utilize dry type plating to obtain by main with chromium form by the nickel-chromium alloy of Addition ofelements the thickness of substrate metal layer less than 5nm, even if via follow-up treatment step, the long-term adaptation of substrate metal layer still there will be problem.Further, if the thickness of substrate metal layer is less than 5nm, then adding the etching solution in man-hour at execution distribution can infiltrate, and causes the situations such as wiring part floats occur, causes the problems such as distribution peel strength obviously reduces to occur, thus not preferred.

On the other hand, if the thickness of substrate metal layer is more than 50nm, then adds man-hour when what implement wiring part, the removing difficulty of substrate metal layer can be caused, and have occur that hair splits, warpage etc. and the situation that causes dhering strength to reduce, thus not preferred.Further, if thickness is thicker than 50nm, then because be difficult to implement etching, thus still not preferred.

The one-tenth of this substrate metal layer is grouped into from thermal endurance and corrosion proof viewpoint, and chromium ratio is necessary for 12 % by weight ~ 22 % by weight.That is, if chromium ratio is less than 12 % by weight, then thermal endurance can be caused to reduce, on the other hand, if chromium ratio is more than 22 % by weight, then when execution wiring part adds man-hour, the removing of substrate metal layer becomes difficulty, thus not preferred.And, in this nickel-chromium alloy, under lifting thermal endurance and corrosion proof order, object characteristic can be coordinated suitably to add transition metal.

To the situation of this substrate metal layer, with regard to 2 layers of flexible substrate of the present invention, the preferred 15nm ~ 50nm of thickness of this substrate metal layer.

Moreover substrate metal layer is preferably 4 % by weight ~ 22 % by weight by chromium ratio, and further containing molybdenum 5 % by weight ~ 40 % by weight, surplus be then the alloy formation of nickel.

Chromium ratio is 4 % by weight ~ 22 % by weight, that to cause heat-resisting peel strength obviously to reduce necessary, if chromium ratio is lower than 4 % by weight, even if then there is molybdenum to add in order to prevent because of heat deterioration, still cannot prevent heat-resisting peel strength from obviously reducing because of heat deterioration, thus not preferred.Further, if chromium ratio is more than 22 % by weight, then etching can be tending towards difficulty, thus not preferred.Therefore, the situation of chromium, more preferably 4 % by weight ~ 15 % by weight, particularly preferably 5 % by weight ~ 12 % by weight.

Secondly, for asking the lifting of corrosion resistance, insulating reliability, molybdenum ratio preferably 5 % by weight ~ 40 % by weight.If molybdenum ratio is less than 5 % by weight, then can not show additive effect, the lifting of corrosion resistance, insulating reliability cannot be presented, thus not preferred.Further, if molybdenum ratio is more than 40 % by weight, then have the tendency that heat-resisting peel strength extremely reduces, thus not preferred.

Moreover, the situation of usually Ni-based alloy target material, if nickel ratio is greater than 93 % by weight, then sputtering target material itself just can become ferromagnetic, when utilizing magnetron sputtering to carry out film forming, film forming speed can be caused to reduce, thus not preferred, and when utilizing sputtering to form substrate metal layer of the present invention, because the target composition nickel amount less than 93 % by weight of sputtering, even if when thus using magnetron sputtering method to carry out film forming, still good rate of film build can be obtained.In addition, in this Ni-Cr-Mo alloy, in lifting thermal endurance and corrosion proof object, object characteristic can be coordinated and suitably add transition metal.

Moreover, in this substrate metal layer, except Ni-Cr-Mo alloy, still can have because being entered etc. and the inevitable impurity of contain less than 1 % by weight by group when target makes.

In addition, be use dry type plating when the formation of substrate metal layer and copper film layer, and in dry type plating, preferably use any one in vacuum vapour deposition, sputtering method or ion plating method.

1-4. insulator film (base material)

Moreover, in 2 layers of flexible substrate of the present invention, the insulator film of base material preferably uses the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

Such as, the insulator film of the thickness 25 ~ 75 μm using film is applicable to.In addition, the inanimate matter materials such as glass fibre, because the obstacle that can become laser processing and chemical etching, thus preferably do not use the substrate containing inanimate matter material.

1-5. layers of copper (conductor layer)

2 layers of flexible substrate of the present invention are after utilizing dry type plating to form copper film layer on substrate metal layer, on this copper film layer, utilize wet type plating to arrange copper wet type plating layer again, lamination is formed with the layers of copper making the thickness containing copper film layer and copper wet type plating layer be 10nm ~ 12 μm.

When only using dry type plating to form layers of copper, dry type plating is any one in vacuum vapour deposition, sputtering method or ion plating method, compared with wet type plating, also has the situation that film forming speed is slow, and is suitable for forming the situation compared with thin copper layer.On the other hand, utilize dry type plating to be formed after copper film layer, then on copper film layer, utilize wet type plating lamination to form layers of copper, be useful in the short time to form thick layers of copper, contribute to productivity and promote.

If 2 layers of flexible substrate most surface of the present invention are copper film layer, then the pinhole number of diameter 5 μm ~ 30 μm is suppressed at every 1 square metre to be less than 45000, if most surface is copper wet type plating layer, be then that the concave defect quantity of 10 μm ~ 20 μm suppresses to be less than 2200 at every 1 square metre by diameter or greatest drawback length, be just applicable to the flexible wiring manufacturing thin space distribution.

The manufacture method of 2.2 layers of flexible substrate

Below, the manufacture method for 2 layers of flexible substrate of the present invention describes in detail.

In the present invention, on single or double to the insulator film of the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film as base material, when not forming substrate metal layer via when bonding agent, and form copper film layer on this substrate metal layer.

The insulator film of base material is normally containing moisture, and must utilize before dry type plating forms the substrate metal layer be made up of nickel-chromium alloy, execution air drying or vacuumize, with the moisture removal will existed in insulator film.If carry out insufficient to this, just can cause being deteriorated with the adaptation of substrate metal layer.

When utilizing dry type plating to form substrate metal layer, such as, when using the coiling type sputter equipment of volume to volume (RolltoRoll) to form substrate metal layer, just the target with substrate metal layer composition is installed on sputtering negative electrode.

First, after implementing vacuum exhaust in the sputter equipment being provided with insulator film, import the mist of nitrogen or argon or nitrogen and argon, and by be held in pressure 0.8Pa ~ 4.0Pa in device inert environments under, apply 1500V ~ 3000V direct voltage or 800V ~ 2000V high frequency voltage between the pairing sparking electrode of plasma electrode, and implement surface treatment at the time utilization plasma of 2 seconds ~ 100 seconds.

Secondly, import argon gas, about 1.3Pa is held in by device, again while by the takers-in in device, lay out the insulator film that roller is installed, transport with the speed of about 3m per minute, while the sputtering direct current power supply electric power connected from negative electrode and carry out sputtering discharge, make in insulator film, form the substrate metal layer be made up of nickel-chromium alloy or Ni-Cr-Mo alloy.

The formation of copper film layer is same with the situation of substrate metal layer, uses and copper target is installed in the sputter equipment on sputtering negative electrode, by copper film layer film forming.Now, substrate metal layer and copper film layer are preferably formed continuously in same vacuum chamber, when after formation substrate metal layer, are taken out in air by film, and when using other sputter equipments to form copper film layer, must implement dehydration fully in advance before film forming.

Moreover, when after utilizing dry type plating to form copper film layer, then when utilizing wet type plating to form copper wet type plating layer on copper film layer, preferably implement such as electroless plating Copper treatment.This non-electrolytic plating process is by forming electroless plating layers of copper on the whole at flexible substrate, even if there is the situation that there is pin hole, still can covers this exposed surface and make flexible substrate face entirety in good conductor, just can suppress the impact reducing pin hole thus.Wherein, when implementing electroless plating Copper treatment, the infiltration caused because of non-electrolytic plating solution and its pretreatment fluid must be noticed and decide condition.

In addition, the thickness of the copper facing wet type plating layer utilizing this non-electrolytic copper plating solution to be formed, as long as be when can because of defect that pin hole causes on repairing substrate face, and when implementing electro-coppering plating solution process, the thickness of the degree can not dissolved because of electro-coppering plating solution, the scope of preferably 0.01 μm ~ 1.0 μm.

So form the substrate of non-electrolytic copper facing wet type plating layer, it is the copper wet type plating layer for final required thickness can be formed, and implement electro-coppering process, just can obtain can not be good by the impact caused because of all size pin hole produced when substrate metal layer is formed, and 2 layers of flexible substrate that adaptation is high.In addition, as long as the electro-coppering process implemented in the present invention is all the condition taking the electrocoppering implemented according to well-established law.

So on substrate metal layer and copper film layer form the thickness of copper wet type plating layer, both made thick also preferred below 12 μm.The reason be set to as this thickness is the distributing board for obtaining narrow wiring width, narrow wiring closet distance.

In addition, whether, be according to the manufacture method of wiring part pattern suitably select if on the surface of copper film layer, utilizing wet type plating to form copper wet type plating layer.

Such as, when utilize known remove method formed wiring part pattern time, be utilize substrate metal layer, copper film layer and copper wet type plating layer formed wiring part, thus must form copper wet type plating layer.To reach the thickness required by wiring part.Herein so-called " removing method ",, in the layers of copper of 2 layers of flexible substrate, resist layer is set on the surface, the mask with set Wiring pattern is set on this resist layer again, irradiation ultraviolet radiation and exposing from the upper side again, through development, to obtain the etching mask being used for unwanted layers of copper etc. being carried out etching, then the layers of copper exposed implemented etching and remove, then again by the method for remaining resist layer removing.Substrate metal layer as the unwanted place of wiring part is also removed by etching, and forms the method for wiring part pattern.

On the other hand, when utilizing semi-additive process to form wiring part pattern, also can utilize wet type plating that copper wet type plating layer is set on Copper thin film groove, also can not arrange.Herein so-called " semi-additive process ", refer to the metal level (metal level be made up of substrate metal layer and copper film layer at 2 layers of flexible substrate, or by substrate metal layer, the metal level that copper film layer and copper wet type plating layer are formed) certain resist layer is set on the surface, the mask with set Wiring pattern is set on this resist layer again, irradiation ultraviolet radiation and exposing from the upper side again, through development, just the plating mask forming wiring part for electro-coppering on layer on surface of metal is obtained, the metal level being exposed to peristome is used as negative electrode, wiring part is formed through plating, then again resist layer is removed, implement soft etching again and the unwanted 2 layers of flexible substrate surface metal except wiring part are removed, the method of wiring part pattern is formed to complete wiring part.

[embodiment]

Below, utilize embodiment to describe the present invention in detail, but the present invention is not limited to these embodiments.The mensuration of each characteristic uses means shown below to implement.

The assay method of pin hole is the laminated body by the substrate metal layer that utilizes dry type plating to obtain and copper film layer, utilization penetrates mode and positions, recycling light microscope determining its size, and the pin hole measuring diameter 5 μm to 30 μm is the number of every 1 square metre.

The appraisal procedure of oligomer amount utilizes oxolane to extract the insulation film after plasma treatment, again extract is used size exclusion chromatography method (SEC method), measure the oligomer ratio of 380 ~ 13500 molecular weight, numerical value before plasma treatment is set to 100%, and compares and conduct " oligomer amount ".

The assay method of peel strength implements according to the method according to IPC-TM-650, NUMBER2.4.9, and as " initial stage peel strength ".Wherein, wire is wide is set to 1mm, and peel angle is set to 90 °.Wire utilizes the method that removes to be formed.Further, the index of thermal endurance the film substrate forming 1mm wire film to be positioned in 150 DEG C of baking boxs 168 hours, after taking-up, being placed to till becoming room temperature, implementing by assessing 90 ° of peel strengths, and as " heat-resisting peel strength ".

The index of moisture-proof is the film substrate by forming 1mm wire film, places 96 hours, being placed to till becoming room temperature, implementing by assessing 90 ° of peel strengths after taking-up in 121 DEG C, 2 atmospheric press heaters, and as " PCT peel strength ".

The assay method of concave defect is for utilizing galvanoplastic to obtain copper wet type plating layer surface, using light microscope to observe, and measure the size of concave defect.

When the situation that concave defect is circular, measure the number of every 1 square metre of diameter 10 μm to 20 μm, when concave defect is situation than circular, then using the defective part length maximum of concave defect as " greatest drawback long ", measure 10 μm of numbers of every 1 square metre to 20 μm of concave defects.

(comparative example 1)

First, comparative example 1 be presented at do not implement plasma treatment situation under implement the characteristic of 2 layers of flexible substrate that film formed.

In thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") one side on form the 1st layer of substrate metal layer, the 1st layer of this substrate metal layer is use 20 % by weight Cr-Ni alloy target material (Sumitomo Metal Mining Co., Ltd's system), DC sputtering is utilized, with film forming speed 0.7nm/sec by 20 % by weight Cr-Ni alloy base metal layer film forming in Ar environment.To an other wherein part according to the same terms film forming, use transmission electron microscope (TEM: Hitachi Ltd.'s system) to measure thickness, result is 0.02 μm.Above-mentioned 20 % by weight Cr-Ni films further form the 2nd layer, 2nd layer is use Cu target (Sumitomo Metal Mining Co., Ltd's system), sputtering method is utilized to form the copper film layer of 100nm thickness, till then recycling copper galvanoplastic film forming to 8 μm thickness.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 471N/m, PCT peel strength is 253N/m, and the pinhole number of dry type substrate is 76714/m ², oligomer amount is 100%, does not obtain sufficient initial stage peel strength.

(embodiment 1)

Below, surface-treated situation insulation film implemented and utilizes plasma treatment is illustrated in.

By thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") be under the environment of 1.6Pa in nitrogen pressure, in between the pairing sparking electrode of plasma electrode, apply 2000V direct voltage 50 second, only plasma treatment is implemented to substrate metal layer film forming face.Then, on plasma treated face, the 1st layer of substrate metal layer is formed at polyimides, the 1st layer of this substrate metal layer is use 20 % by weight Cr-Ni alloy target material (Sumitomo Metal Mining Co., Ltd's system), DC sputtering is utilized, with film forming speed 0.7nm/sec by 20 % by weight Cr-Ni alloy base metal layer film forming in Ar environment.

To an other wherein part according to the same terms film forming, use transmission electron microscope (TEM: Hitachi Ltd.'s system) to measure thickness, result is 0.02 μm.This 20 % by weight Ni-Cr film further forms the 2nd layer, and the 2nd layer is use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then recycles copper galvanoplastic film forming to 8 μm thickness.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 624N/m, PCT peel strength is 434N/m, the dry type plating (laminated body of substrate metal layer and copper film layer.Hereinafter referred to as " dry type plating ") pinhole number be 36443/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%, and concave defect number is 1951/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 2)

By thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 2.4Pa, in between the pairing sparking electrode of plasma electrode, apply 2000V direct voltage 50 second, only plasma treatment is implemented to substrate metal layer film forming face.Then, on plasma treated face, the 1st layer of substrate metal layer is formed at polyimides, the 1st layer of this substrate metal layer is use 20 % by weight Cr-Ni alloy target material (Sumitomo Metal Mining Co., Ltd's system), DC sputtering is utilized, with film forming speed 0.7nm/sec by 20 % by weight Cr-Ni alloy base metal layer film forming in Ar environment.To an other wherein part according to the same terms film forming, use transmission electron microscope (TEM: Hitachi Ltd.'s system) to measure thickness, result is 0.02 μm.This 20 % by weight Ni-Cr film further forms the 2nd layer, and the 2nd layer is use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then recycles copper galvanoplastic film forming to 8 μm thickness.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 635N/m, PCT peel strength is 463N/m, and the pinhole number of dry type plating is 15571/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 56%, and concave defect number is 1645/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 3)

By thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 3.1Pa, in between the pairing sparking electrode of plasma electrode, apply 2000V direct voltage 50 second, only plasma treatment is implemented to substrate metal layer film forming face.Then, on plasma treated face, the 1st layer of substrate metal layer is formed at polyimides, the 1st layer of this substrate metal layer is use 20 % by weight Cr-Ni alloy target material (Sumitomo Metal Mining Co., Ltd's system), DC sputtering is utilized, with film forming speed 0.7nm/sec by 20 % by weight Cr-Ni alloy base metal layer film forming in Ar environment.To an other wherein part according to the same terms film forming, use transmission electron microscope (TEM: Hitachi Ltd.'s system) to measure thickness, result is 0.02 μm.Above-mentioned 20 % by weight Cr-Ni films further form the 2nd layer, and the 2nd layer is use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then recycles copper galvanoplastic film forming to 8 μm thickness.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 632N/m, PCT peel strength is 467N/m, and the pinhole number of dry type plating is 8236/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 50%, and concave defect number is 2005/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(comparative example 2)

Though for by thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 0.7Pa, in between the pairing sparking electrode of plasma electrode, apply 500V direct voltage 15 second, but electric discharge is in unstable, and cannot processes.

(comparative example 3)

Though by thickness 38 μm of polyimide films (Dong Li E.I.Du Pont Company system, registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 4.7Pa, in between the pairing sparking electrode of plasma electrode, apply 3500V direct voltage 6 second and implement plasma treatment, but surface occurs wrinkling, follow-up characteristic evaluation is caused to carry out.

(embodiment 4)

Except being set to Ar Pressure 3.6Pa, and plasma electrode applies direct current 2800V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 4 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 612N/m, and the pinhole number of dry type plating is 7428/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 50%, and concave defect number is 889/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 5)

Except being set to Ar Pressure 1.6Pa, and plasma electrode applies direct current 2200V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 5 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 627N/m, and the pinhole number of dry type plating is 5142/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%.In addition, the concave defect of 2 layers of flexible substrate that embodiment 5 relates to measures not to be implemented.

(embodiment 6)

Except being set to Ar Pressure 3.6Pa, and plasma electrode applies direct current 1600V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 6 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 626N/m, and the pinhole number of dry type plating is 6428/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%.In addition, the concave defect of 2 layers of flexible substrate that embodiment 6 relates to measures not to be implemented.

(comparative example 4)

Though be set to Ar Pressure 0.7Pa, and apply the direct current 500V in 6 seconds for plasma electrode, electric discharge in unstable, and cannot process.

(comparative example 5)

Though be set to Ar Pressure 4.7Pa, and plasma electrode apply direct current 3500V and implement 6 second plasma treatment, surface occurs wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 7)

Except the mixed pressure 1.6Pa being set to 75 volume % argon-25 volume % nitrogen, and plasma electrode applies direct current 1800V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 7 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 608N/m, and the pinhole number of dry type plating is 8571/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%, and concave defect number is 1855/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 8)

Except the mixed pressure 1.6Pa being set to 75 volume % argon-25 volume % nitrogen, and plasma electrode applies direct current 2300V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 8 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 599N/m, and the pinhole number of dry type plating is 7143/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 50%, and concave defect number is 1554/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 9)

Except the mixed pressure 3.6Pa being set to 75 volume % argon-25 volume % nitrogen, and plasma electrode applies direct current 1500V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 9 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 593N/m, and the pinhole number of dry type plating is 24000/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 60%, and concave defect number is 1762/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(comparative example 6)

Though be set to the mixed pressure 0.7Pa of 75 volume % argon-25 volume % nitrogen, and apply the direct current 500V in 6 seconds for plasma electrode, electric discharge in unstable, and cannot process.

(comparative example 7)

Though be set to the mixed pressure 4.7Pa of 75 volume % argon-25 volume % nitrogen, and plasma electrode apply direct current 3500V and implement 6 second plasma treatment, surface occurs wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 10)

Except the mixed pressure 1.6Pa being set to 50 volume % argon-50 volume % nitrogen, and plasma electrode applies direct current 3000V and implements outside 50 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 10 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 681N/m, and the pinhole number of dry type plating is 18276/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%, and concave defect number is 2076/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 11)

Except the mixed pressure 1.6Pa being set to 50 volume % argon-50 volume % nitrogen, and plasma electrode applies direct current 1800V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 11 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 572N/m, and the pinhole number of dry type plating is 15286/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 30%, and concave defect number is 1861/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 12)

Except the mixed pressure 3.6Pa being set to 50 volume % argon-50 volume % nitrogen, and plasma electrode applies direct current 2000V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 12 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 583N/m, and the pinhole number of dry type plating is 21286/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 40%, and concave defect number is 1889/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(comparative example 8)

Though be set to the mixed pressure 0.7Pa of 50 volume % argon-50 volume % nitrogen, and apply the direct current 500V in 6 seconds for plasma electrode, electric discharge in unstable, and cannot process.

(comparative example 9)

Though be set to the mixed pressure 4.7Pa of 50 volume % argon-50 volume % nitrogen, and plasma electrode apply direct current 3500V and implement 6 second plasma treatment, surface occurs wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 13)

Except the mixed pressure 1.6Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies direct current 1600V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 13 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 586N/m, and the pinhole number of dry type plating is 8857/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 55%, and concave defect number is 1428/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 14)

Except the mixed pressure 1.6Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies direct current 1800V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 14 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 567N/m, and the pinhole number of dry type plating is 11569/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 50%, and concave defect number is 1276/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 15)

Except the mixed pressure 3.6Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies direct current 2000V and implements outside 6 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 15 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 584N/m, and the pinhole number of dry type plating is 22429/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%, and concave defect number is 1987/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(comparative example 10)

Though be set to the mixed pressure 0.7Pa of 25 volume % argon-75 volume % nitrogen, and apply the direct current 500V in 6 seconds for plasma electrode, electric discharge in unstable, and cannot process.

(comparative example 11)

Though be set to the mixed pressure 4.7Pa of 25 volume % argon-75 volume % nitrogen, and plasma electrode apply direct current 3500V and implement 6 second plasma treatment, surface occurs wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 16)

Except the mixed pressure 1.6Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 16 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 598N/m, and the pinhole number of dry type plating is 9847/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 65%, and concave defect number is 1564/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 17)

Except the mixed pressure 1.6Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies high frequency 1000V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 17 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 608N/m, and the pinhole number of dry type plating is 15098/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 63%, and concave defect number is 2017/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 18)

Except the mixed pressure 2.4Pa being set to 25 volume % argon-75 volume % nitrogen, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 18 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 614N/m, and the pinhole number of dry type plating is 19713/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 70%, and concave defect number is 1798/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(comparative example 12)

Though be set to the mixed pressure 0.3Pa of 25 volume % argon-75 volume % nitrogen, and apply the high frequency 600V in 12 seconds for plasma electrode, electric discharge in unstable, and cannot process.

(comparative example 13)

Though be set to the mixed pressure 4.7Pa of 25 volume % argon-75 volume % nitrogen, and plasma electrode apply high frequency 600V and implement 12 second plasma treatment, surface occurs wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 19)

Except being set to Ar Pressure 1.6Pa, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 19 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 598N/m, and the pinhole number of dry type plating is 25673/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 56%, and concave defect number is 1897/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 20)

Except the mixed pressure 1.6Pa being set to 75 volume % argon-25 volume % nitrogen, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 20 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 587N/m, and the pinhole number of dry type plating is 19476/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 66%, and concave defect number is 1674/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 21)

Except the mixed pressure 1.6Pa being set to 50 volume % argon-50 volume % nitrogen, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 21 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 569N/m, and the pinhole number of dry type plating is 24384/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 62%, and concave defect number is 1720/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

(embodiment 22)

Except being set to nitrogen pressure 1.6Pa, and plasma electrode applies high frequency 600V and implements outside 12 second plasma treatment, and all the other make 2 layers of flexible substrate that embodiment 22 relates to all similarly to Example 1.

The initial stage peel strength of the 2 layers of flexible substrate obtained is 601N/m, and the pinhole number of dry type plating is 27846/m ², and there is no the pin hole of diameter more than 30 μm, oligomer amount is 59%, and concave defect number is 2008/m ², and there is no diameter or the long concave defect more than 20 μm of greatest drawback.

The result of above-described embodiment, comparative example arranges as shown in table 1.

As shown in Table 1, by implementing the surface treatment according to the plasma treatment of institute of the present invention fixed condition to insulator film, the oligomer amount of insulator film can be made to become less than 70% of the oligomer amount before surface treatment, and the pinhole number of dry type plating can be suppressed at 45000/m ²below, and can by the concave defect number of copper wet type plating layer suppress at 2200/m ²under.

Further, when the ambient pressure of surface-treated plasma treatment is less than 0.8Pa, confirms electric discharge in unstable, and surface treatment cannot be implemented to insulator film.If further, also learn that the applying voltage for plasma electrode is too high, then insulator film there will be wrinkling, cause manufacturing 2 layers of flexible substrate.

Claims

1.2 layers of flexible substrate, it is at least one side of insulator film, in not via bonding agent when, utilizes dry type plating to form substrate metal layer, this substrate metal layer utilizes dry type plating form copper film layer; It is characterized by,

Above-mentioned insulator film is that only implementing the oligomer amount after above-mentioned surface treatment to the one side of above-mentioned insulator film, is less than 70% of the oligomer amount before surface treatment at least simultaneously implementing surface treatment;

Above-mentioned copper film layer is following copper film layer: in the oligomer amount on surface be less than 70% above-mentioned insulator film on arrange, the thickness with 50nm ~ 500nm, and do not have the pin hole of diameter more than 30 μm, and diameter more than 5 μm and the pin hole of less than 30 μm is every 1 square metre less than 45000.

2. 2 layers of flexible substrate of claim 1 record, wherein, above-mentioned copper film layer utilize wet type plating form copper wet type plating layer.

3. 2 layers of flexible substrate of claim 2 record, wherein, above-mentioned copper wet type plating layer has the thickness of 0.5 μm ~ 12 μm, and there is no the long concave defect more than 20 μm of diameter or greatest drawback, and diameter or greatest drawback long more than 10 μm and the concave defect of less than 20 μm is every 1 square metre less than 2200.

4. the 2 layers of flexible substrate recorded any one of claims 1 to 3, wherein, above-mentioned substrate metal layer has the thickness of 5nm ~ 50nm, formed by containing nickel-chromium alloy, described nickel-chromium alloy be Addition ofelements 6 % by weight ~ 22 % by weight surplus based on chromium then by nickel is formed, and the thickness of the conductor layer (layers of copper) be made up of copper film layer and copper wet type plating layer set on above-mentioned substrate metal layer is 50nm ~ 12 μm.

5. the 2 layers of flexible substrate recorded any one of claims 1 to 3, wherein, above-mentioned insulator film is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

6. 2 layers of flexible substrate of claim 4 record, wherein, above-mentioned insulator film is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

7. the 2 layers of flexible substrate recorded any one of claims 1 to 3, wherein, above-mentioned surface treatment implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 1500V ~ 3000V direct voltage under the inert environments of pressure 0.8Pa ~ 4.0Pa.

8. 2 layers of flexible substrate of claim 4 record, wherein, above-mentioned surface treatment implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 1500V ~ 3000V direct voltage under the inert environments of pressure 0.8Pa ~ 4.0Pa.

9. 2 layers of flexible substrate of claim 5 record, wherein, above-mentioned surface treatment implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 1500V ~ 3000V direct voltage under the inert environments of pressure 0.8Pa ~ 4.0Pa.

10. 2 layers of flexible substrate of claim 6 record, wherein, above-mentioned surface treatment implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 1500V ~ 3000V direct voltage under the inert environments of pressure 0.8Pa ~ 4.0Pa.

2 layers of flexible substrate that 11. claims 7 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 12. claims 8 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 13. claims 9 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 14. claims 10 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

The 2 layers of flexible substrate recorded any one of 15. claims 1 to 3, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa ~ 4.0Pa, implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 800V ~ 2000V high frequency voltage.

2 layers of flexible substrate that 16. claims 4 are recorded, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa ~ 4.0Pa, implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 800V ~ 2000V high frequency voltage.

2 layers of flexible substrate that 17. claims 5 are recorded, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa ~ 4.0Pa, implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 800V ~ 2000V high frequency voltage.

2 layers of flexible substrate that 18. claims 6 are recorded, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa ~ 4.0Pa, implements to the surface of above-mentioned insulator film the plasma discharge process utilizing 800V ~ 2000V high frequency voltage.

2 layers of flexible substrate that 19. claims 15 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 20. claims 16 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 21. claims 17 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

2 layers of flexible substrate that 22. claims 18 are recorded, wherein, above-mentioned surface-treated inert environments is nitrogen environment, and the PCT peel strength after surface treatment is more than 70% of initial stage peel strength.

The manufacture method of 23.2 layers of flexible substrate, it is at least one side of insulator film, in not via bonding agent when, utilize dry type plating to form substrate metal layer, above-mentioned substrate metal layer utilizes dry type plating form copper film layer, described copper film layer has the thickness of 50nm ~ 500nm, and there is no the pin hole of diameter more than 30 μm, and diameter more than 5 μm and the pin hole of less than 30 μm is every 1 square metre less than 45000, it is characterized by

To the surface of above-mentioned insulator film under the inert environments of pressure 0.8Pa ~ 4.0Pa, execution utilizes the surface treatment applying the plasma discharge in 2 ~ 100 seconds between the pairing sparking electrode of plasma electrode, make the oligomer amount on surface be after less than 70%, form substrate metal layer.

The manufacture method of 2 layers of flexible substrate that 24. claims 23 are recorded, wherein, the above-mentioned surface treatment utilizing plasma discharge, be plasma electrode sparking electrode between apply 1500V ~ 3000V direct voltage.

The manufacture method of 2 layers of flexible substrate that 25. claims 23 are recorded, wherein, the above-mentioned surface treatment utilizing plasma discharge, be plasma electrode sparking electrode between apply 800V ~ 2000V high frequency voltage.

The manufacture method of 26.2 layers of flexible substrate, it is the manufacture method of the 2 layers of flexible substrate recorded any one of claim 11 ~ 14, on at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, above-mentioned substrate metal layer utilizes dry type plating form copper film layer, it is characterized by

To the surface of above-mentioned insulator film under the nitrogen environment of pressure 0.8Pa ~ 4.0Pa, implement to utilize and apply 1500V ~ 3000V direct voltage 2 ~ 100 second between the pairing sparking electrode of plasma electrode and after the surface treatment of plasma that produces, form substrate metal layer.

The manufacture method of 27.2 layers of flexible substrate, it is the manufacture method of the 2 layers of flexible substrate recorded any one of claim 19 ~ 22, on at least one side of insulator film, in not via bonding agent when, dry type plating is utilized to form substrate metal layer, above-mentioned substrate metal layer utilizes dry type plating form copper film layer, it is characterized by

To the surface of above-mentioned insulator film under the nitrogen environment of pressure 0.8Pa ~ 4.0Pa, implement to utilize and apply 800V ~ 2000V high frequency voltage 2 ~ 100 second between the pairing sparking electrode of plasma electrode and after the surface treatment of plasma that produces, form substrate metal layer.

The manufacture method of the 2 layers of flexible substrate recorded any one of 28. claims 23 to 27, wherein, above-mentioned dry type plating is any one in vacuum vapour deposition, sputtering method and ion plating method.

The manufacture method of the 2 layers of flexible substrate recorded any one of 29. claims 23 to 27, wherein, above-mentioned insulator film is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.

The manufacture method of 2 layers of flexible substrate that 30. claims 28 are recorded, wherein, above-mentioned insulator film is the resin film selected from polyimides system film, polyamide-based film, ployester series film, polytetrafluoroethylene system film, polyphenylene sulfide system film, PEN system film, polymerizable mesogenic system film.