CN102792786A

CN102792786A - Two-layer flexible substrate and process for producing same

Info

Publication number: CN102792786A
Application number: CN2011800138707A
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: 2012-11-21
Anticipated expiration: 2031-03-10
Also published as: TW201139730A; JPWO2011114997A1; WO2011114997A1; KR20120127743A; KR101363771B1; JP5672299B2; TWI510673B; CN102792786B

Abstract

Provided is a two-layer flexible substrate, in particular, a two-layer flexible substrate suitable for fine-pattern formation or COF mounting, which not only has no pinholes of a thin copper film layer or a copper layer that are due to pinholes generated when an undercoat metal layer was formed on an insulator film by dry plating, but also has few pinholes of the undercoat metal layer, and which has excellent adhesion between the insulator film and the undercoat metal layer and excellent corrosion resistance and water resistance. Also provided is a process for producing the two-layer flexible substrate. The two-layer flexible substrate is obtained by forming an undercoat metal layer by dry plating on at least one surface of an insulator film without through any adhesive and forming a thin copper film layer and/or a copper layer on the undercoat metal layer by dry plating. The insulator film had undergone a surface treatment, and the insulator film after the surface treatment had an oligomer amount that was up to 70% of the oligomer amount of the insulator film which had not undergone the surface treatment.

Description

2 layers of flexible substrate and manufacturing approach thereof

[technical field]

The invention relates to 2 layers of flexible substrate and manufacturing approach thereof; More specifically; Be about when on insulator film, forming substrate metal layer (following also claim sometimes " Seed Layer ") according to dry type plating method, when then forming the copper layer again, 2 layers of flexible substrate that pin hole and concave defect are few and manufacturing approach thereof.

[background technology]

Now LCD, mobile phone, digital camera and various electronic instruments etc. are required slim, small-sized, lightweight; The electronic component that is carried above that has the trend towards miniaturization, and supply to form the substrate that electronic circuit uses and have: hard tabular " rigidity printing distributing board " but and " flexible printing distributing board (following also claim sometimes " FPC ") " of film like and tool flexibility and free bend.

Particularly FPC utilizes its flexibility; Can be used in such as: lcd driver requires the place of tortuosity with the hinge that kind of distributing board, HDD (hard disk drive), DVD (numberization multifunctional optical disk) module, mobile phone, thereby this demand will increase day by day.

What use as this FPC material is on insulation films such as polyimides, polyester, is pasting the copper-surfaced laminated plate (following also claim sometimes " CCL ") 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 paste (claims " 3 layers of CCL " usually; To call " 3 layers of CCL " in the following text); Another is that insulation film and Copper Foil (conductor layer) are not using under the situation of bonding agent; Utilize casting method, layered manner, metallization etc. directly to carry out compound CCL (claiming " 2 layers of CCL " usually) to call " 2 layers of CCL " in the following text.

If should " 3 layers of CCL " and " 2 layers of CCL " compare, with regard to manufacturing cost, because 3 layers of CCL is easy at manufacture views such as the fee of material of insulation film, bonding agent etc., operability, thereby cheap.On the other hand, with regard to characteristics such as thermal endurance, filmization, dimensional stability, then be 2 layers of CCL excellence, receive the fine patterning of circuit, the influence of high-density installationization, though belong to high unit price, 2 layers of CCL demand of slimming enlarge gradually.

Moreover, be that the COF that utilizes the light that sees through insulator film to detect the IC position again is installed as main flow, and requires the thinness of material itself and the transparency of insulating material with after forming Wiring pattern on the CCL in the method that IC is installed on the FPC.Put also is that 2 layers of CCL are favourable at this point.

Manufacturing approach with 2 layers of CCL of such characteristic roughly can be categorized as 3 kinds.The 1st kind is on electrolytic copper foil or rolled copper foil, to utilize casting method to paste the method for insulation film.The 2nd kind is on insulation film, to utilize layered manner to paste the method for electrolytic copper foil or rolled copper foil.The third is on insulation film, to utilize dry type plating method (so-called " dry type plating method " is meant sputtering method, ion plating method, group's ion beam (cluster ion beam) method, vacuum vapour deposition, CVD method etc.) here; The substrate metal layer of film is set on insulation film, and face carries out electro-coppering and forms the method for copper layer on it again.Usually the third method is called " metallization ".

Because this metallization is through use dry type plating method and wet type plating method (for example electroplating), and can freely control this metal layer thickness, thereby with regard to the filmization of metal level, is in a ratio of easily with casting method or layered manner.Also have,, thereby it is generally acknowledged and be applicable to fine pattern because the flatness at polyimides and metal level interface is high.

But the CCL that utilizes metallization to obtain because the metal-insulator film interface is level and smooth, thereby the anchoring effect that generally utilized of bonding between metal and insulation film and can't expecting, and has the problem that the dhering strength at interface can't fully manifest.

Promptly; Use the formed 2 layers of CCL of this metallization; If be implemented in 121 ℃, 95%RH, 2 atmospheric high temperature, high humidity, long-time down " PCT test (the Pressure Cooker Test; high pressure aqueous vapor test) " that place of high pressure, to compare with the initial stage dhering strength, the tendency that dhering strength significantly reduces can appear.Thereby; If when considering dry after pattern forms the liquid resist-coated in the step; Can be applied in the heat about 100～150 ℃; And the joint when IC etc. is installed on formation pattern also can apply the heat about 250 ℃ during with welding; And will be the distribution that forms of pattern utilize items such as sealing resin such as solder resist seals, known according to the metallization manufacturing 2 layers of CCL and be not suitable for that fine pattern high temperature under forms, the COF installation, cause the lifting of thermal endurance, moisture-proof to necessitate and obligato problem.

As solution to problem like this; Be that for example patent documentation 1 motion has: forming with Ni, Cr is the method for the metal alloy layer of principal component as the intermediate layer (Seed Layer) of insulation film and copper layer; But when forming more fine pattern, just must improve its moisture-proof more.

Moreover; Patent documentation 2 records following method: directly having by copper or with copper on the single face at least of plastic film substrate is that the alloy of principal component constitutes among the flexible printed wiring board of copper film; This copper film is to hold: 2 layers of structure that have the superficial layer of crystalline texture and between this superficial layer and plastic film substrate, be provided with the bottom surface layer of polycrystalline structure; And the X ray of copper film is resolved in the pattern; The peak intensity of lattice plane index (200) is below 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 is that utilization is used the Cement Composite Treated by Plasma of nitrogenous mist and on the plastic film substrate, generated the functional group; And form by copper or with copper is the metal that alloy constituted of principal component, carries out chemical bonding through this metal with the atom that constitutes the plastic film substrate and constitutes, thereby promote moisture-proof.Yet this invention is the control that relies on lattice plane, reaches with the composite effect that is produced by Cement Composite Treated by Plasma, but controls this lattice plane difficulty technically, is difficult to stably produce in a large number.

Yet; Be film forming substrate metal layer on insulator film; Generally be to use vacuum vapour deposition, sputtering method, ion plating method etc.; But because the pin hole that can be produced a plurality of tens of μ m～hundreds of μ m size by rete usually that is obtained according to this dry type plating method, thereby substrate metal layer tends to occur the insulator film exposed portions serve that causes because of this pin hole.

At present; In this flexible wiring; The thickness of the needed copper conductive cell envelope of distribution be surpass 35 μ m and till the 50 μ m for appropriate, but because the width of the distribution that forms also has about hundreds of μ m, so seldom can cause wiring part generation defective because of the existence of ten μ m pin holes.

Yet; When desire obtain target of the present invention have in a narrow margin the flexible wiring with the wiring part of thin space the time; As aforementioned; The thickness that is preferred for the copper tunicle that wiring part forms is below the 15 μ m, more preferably below the 8 μ m, ideal is the very narrow thickness about 5 μ m, the possibility that causes wiring part to produce defective improves.

If to this situation; So that be used on the insulator film that is formed with substrate metal layer form desired thickness copper by 2 layers of flexible substrate of rete; Utilization removes method (subtractive method), and to carry out the situation of flexible wiring manufacturing be that example describes, and then the formation of wiring part pattern is to implement according to following step.

(1) resist layer of the required wiring part pattern with the copper conductor layer that only covers wiring part but expose non-wiring part is set on the copper conductor layer.

(2) the copper conductor layer that exposes being implemented chemical etching handles and removes.

(3) resist layer is peeled off removed at last.

Therefore; When use for example be formed with 5 μ m as thin as a wafer copper by the substrate of thicknesses of layers; When making wide 15 μ m of distribution for example, wiring closet apart from the distributing board of wide, the narrow wiring closet distance of narrow distribution of 30 μ m; Handling because of the dry type plating in the pin hole that on the substrate metal layer of substrate, is produced, thick big young pathbreaker reaches tens of μ m to hundreds of μ m grades, thereby when forming the electro-coppering tunicle of 5 μ m left and right thicknesses; Because of the insulator film exposed portions serve that pin hole caused almost can't be buried; So this exposed portions serve (being the damaged part of conductor layer) can involve wiring part, cause wiring part to occur damaged and become the distribution defective in the pin hole position, both having made not is can become the reason that causes the wiring part driving fit bad so yet.

Therefore, patent documentation 3 discloses: the technology of the pinhole number of regulation metal salt/polyimide thin-film laminate.But the pin hole of patent documentation 3 and non-public vapor-deposited film, but the pin hole after the regulation electro-coppering do not have any mentioning about the pin hole of vapor-deposited film and substrate metal layer.

Moreover; As solution to the problems described above; Patent documentation 4 records: on insulator film, utilize dry type plating method to form substrate metal layer; And then bestow and utilize the deposited copper coating of electroless plating as intermediate metal layer, will be because of the method for the insulator film exposed portions serve lining that pin hole caused.

But; Though this method can be eliminated the insulator film exposed portions serve that causes because of pin hole really to a certain degree; But then; Employed plating solution and its pretreatment fluid etc. when electroless plating copper is handled have been learnt; Can partly infiltrating between insulator film and the substrate metal layer from established size pin hole miscellaneous, the reason that this might become the adaptation of substrate metal layer and utilize the conductor layer adaptation formation obstruction due to institute's electro-coppering that forms afterwards is not sufficient solution countermeasure.Also have, even if but utilize electro-coppering buried insulation body thin film exposed portions serve, but because insulation film is low with the closing force of copper interlayer, thereby if substrate metal layer has pin hole, just can becomes and cause the bad reason with the insulating reliability reduction of driving fit.

[prior art document]

[patent documentation]

Patent documentation 1: Japanese Patent Laid is opened the 2006-13152 communique

Patent documentation 2: No. the 3563730th, Japan Patent

Patent documentation 3: japanese patent laid-open 11-92917 communique

Patent documentation 4: japanese patent laid-open 10-195668 number

[summary of the invention]

Invent problem to be solved

The problems referred to above when the objective of the invention is to solve 2 layers of flexible substrates manufacturing using dry type plating method; And provide: do not have the pin hole that is produced when on insulator film, utilizing the dry type plating handle to form substrate metal layer and cause the damaged of Copper Foil rete and copper layer; Substrate metal layer damaged 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 forms, COF installs, and manufacturing approach.

The means that are used to deal with problems

The inventor etc. find through using on the single face at least of insulator film; Under situation not, utilize dry type plating method to form substrate metal layer, and on this substrate metal layer, form the copper film layer of required bed thickness and/or 2 layers of flexible substrate of copper layer via bonding agent; Wherein, This insulator film is through implementing surface-treated, and the oligomer amount is 2 layers of flexible substrate 70% below of the oligomer amount before the surface treatment, and the pin hole that is produced in the time of just can obtaining not have because of the formation substrate metal layer causes the damaged of copper film layer and copper layer; And substrate metal layer is damaged also few; And the adaptation of insulator film and base metal interlayer, corrosion resistance, and 2 layers of all excellent flexible substrate of resistance to water, also applicable to have in a narrow margin, the flexible wiring of the wiring part of thin space, thereby accomplish the present invention.

The present invention the 1st invention is 2 layers of flexible substrate, and it is on the single face at least of insulator film, under the situation via bonding agent not; Utilize dry type plating method to form substrate metal layer; On this substrate metal layer, utilize dry type plating method to form 2 layers of flexible substrate of copper film layer, wherein, insulator film is at least simultaneously implementing surface treatment;, be below 70% of oligomer amount before the surface treatment only to the oligomer amount after this surface treatment of one side execution of insulator film.

The present invention the 2nd invention is that the copper film layer of the 1st invention has the thickness of 50nm～500nm, and does not have diameter to surpass the pin hole of 30 μ m, and diameter 5 μ m pin hole above and below the 30 μ m is per 1 square metre below 45000.

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

The present invention's the 4th invention is that the copper wet type plating layer of the 3rd invention has 0.5 μ m～12 μ m thickness; And the concave defect that does not have the long 20 μ m of surpassing of diameter or greatest drawback, and diameter or the long 10 μ m of greatest drawback concave defect above and below the 20 μ m are per 1 square metre below 2200.

The present invention's the 5th invention is 2 layers of flexible substrate of the 1st to the 4th invention; Wherein, Substrate metal layer has 5nm～50nm bed thickness; Form by containing nickel-chromium alloy, said nickel-chromium alloy is to be that main interpolation element 6 weight %～22 weight % surpluses are then constituted by nickel with chromium, and the bed thickness of the set conductor layer (copper layer) that is made up of copper film layer and copper wet type plating layer is 50nm～12 μ m on substrate metal layer.

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

The present invention's the 7th invention is that the surface treatment of the 1st to the 6th invention is under the inert environments of pressure 0.8Pa～4.0Pa, the plasma discharge that utilizes 1500V～3000V direct voltage to be implemented on the surface of insulator film to handle.

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

The present invention's the 9th invention is that the surface treatment of the 1st to the 6th invention is under the inert environments of pressure 0.8Pa～4.0Pa, the plasma discharge that utilizes 800V～2000V high frequency voltage is implemented on the surface of insulator film handled.

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

The present invention's the 11st invention is on the single face at least of insulator film; Under situation not via bonding agent; Utilize dry type plating method to form substrate metal layer; On above-mentioned substrate metal layer, utilize dry type plating method to form the manufacturing approach 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; After execution utilizes the surface treatment of the plasma discharge that applied for 2～100 seconds between the pairing sparking electrode of article on plasma body electrode, form substrate metal layer.

The present invention the 12nd invention is the surface treatment that utilizes plasma discharge of the 11st invention, is to apply 1500V～3000V direct voltage between the sparking electrode of article on plasma body electrode.

The present invention the 13rd invention is the surface treatment that utilizes plasma discharge of the 11st invention, is to apply 800V～2000V high frequency voltage between the sparking electrode of article on plasma body electrode.

The present invention's the 14th invention is the manufacturing approach of 2 layers of flexible substrate of the 8th invention; On the single face at least of insulator film; Under situation not via bonding agent, utilize dry type plating method to form substrate metal layer, on this substrate metal layer, utilize dry type plating method to form copper film layer; Wherein, To the surface of insulator film under the nitrogen environment of pressure 0.8Pa～4.0Pa, implement the surface treatment of the plasma that applies 1500V～2～100 seconds of 3000V direct voltage between the pairing sparking electrode that utilizes article on plasma body electrode and produce after, form substrate metal layer.

The present invention's the 15th invention is the manufacturing approach of 2 layers of flexible substrate of the 10th invention; On the single face at least of insulator film; Under situation not via bonding agent, utilize dry type plating method to form substrate metal layer, on this substrate metal layer, utilize dry type plating method to form copper film layer; Wherein, To the surface of insulator film under the nitrogen environment of pressure 0.8Pa～4.0Pa, implement the surface treatment of the plasma that applies 800V～2～100 seconds of 2000V high frequency voltage between the pairing sparking electrode that utilizes article on plasma body electrode and produce after, form substrate metal layer.

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

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

(invention effect)

According to the present invention; Copper film layer and copper wet type plating layer that the pin hole that is produced in the time of can obtaining not have because of the formation substrate metal layer causes are damaged; The damaged of substrate metal layer also lacked, and the adaptation of insulator film and substrate metal layer and 2 layers of all excellent flexible substrate of corrosion resistance.These 2 layers of flexible substrates also be applicable to have in a narrow margin, the flexible wiring of thin space wiring part, thereby performance significant effect in industry.

[embodiment]

1.2 layer flexible substrate

2 layers of flexible substrate of the present invention are on the single face at least of insulator film; Under situation not via bonding agent; Utilize dry type plating method 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 through implementing surface treatment, and makes the oligomer amount become the oligomer amount below 70% of the oligomer amount before surface treatment; Through insulator film is implemented surface treatment, compare with the oligomer amount before the surface treatment, make the surface of the oligomer amount that becomes below 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 do not have the pin hole of diameter 30 μ m, and the pin hole of diameter 5 μ m to 30 μ m is to be below 45000 at per 1 square metre.

1-1. copper film layer

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

If the not enough 50nm of the thickness of this Copper Foil rete, when utilizing follow-up electrocoppering as one of wet type plating method on the copper film layer surface, to implement the film forming of copper wet type plating layer, the resistance value of copper film layer can improve, and can make the plating appearance degradation of copper laminar surface.In addition, when utilizing electrocoppering to carry out the film forming of copper wet type plating layer, copper film layer is to bring into play 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 surpasses 500nm and carries out film forming, though then the pin hole between the copper film has minimizing, this is utilizing dry type plating method the copper film layer film forming is consuming time, less economical.

Generally speaking, copper film layer and copper wet type plating layer are that pin hole can grown up and bury to the copper of thick more then institute film forming more, thereby pin hole is little, even can tail off.So, compare with dry type plating method, utilize the fast wet type plating method of film forming speed that copper wet type plating layer is set on the copper film layer surface, and make 2 layers of flexible substrate.These 2 layers of flexible substrates are to utilize the wet type plating to make its surperficial pinhole number become small.But even if the pin holes on 2 layers of flexible substrate surface are buried, but the pin hole of substrate metal layer and copper film layer is the state of not buried.

So; If under the situation of aperture size that does not suppress substrate metal layer and copper film layer and quantity; Form the wiring part pattern of narrow wiring closet distance; Wiring part does not have convenient can the exposing of ground of substrate metal layer, causes becoming the distribution defective, even if really not soly can become the reason that causes the wiring part driving fit bad yet.

Moreover; Buried though the pin hole of copper film layer utilizes the wet type plating, if the pin hole of copper film layer is arranged, then substrate metal layer just can be exposed in the atmosphere before the wet type plating; Thereby substrate metal layer just can go bad, and causes becoming distribution defective, and the bad reason of wiring part driving fit.

Thereby, in the copper film layer of the present invention,, also be that size is in the scope below 45000 at per 1 square metre preferably for the pin hole of diameter 5 μ m～30 μ m even if having pin hole.In addition, the pin hole of diameter less than 5 μ m is because cause distribution defective, driving fit condition of poor few, and detects also difficulty, thereby and unspecified quantity.

Through using above-mentioned formation; Just can obtain not have the pin hole that is produced when forming substrate metal layer and cause copper damaged by membranous part; And substrate metal layer is damaged few, and the adaptation of insulator film and substrate metal layer, corrosion resistance, and 2 layers of all excellent flexible substrate of resistance to water.

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

Surface treatment to the insulator film of base material is to use Cement Composite Treated by Plasma to implement.Surface treatment is to implement the single face of insulator film, but two-sided enforcement is had more effect.

Treatment conditions are under the inert environments, the pressure of 0.8Pa～4.0Pa.Under the inert environments of insufficient pressure 0.8Pa, it is stable that plasma discharge is difficult for being, strong because processing can become if under the inert environments that surmounts pressure 4.0Pa, thereby have when handling and cause insulation film wrinkling situation to occur, so not preferred.

Between the pairing sparking electrode of plasma electrode, apply the direct voltage of 1500V～3000V, handle and implement direct-current plasma (DC plasma).If the not enough 1500V of this direct voltage; Then utilize a little less than the processing excessively of plasma execution, can't show the rising of initial stage dhering strength, if surpass 3000V; Then because processing can become strong; Thereby cause when handling insulation film wrinkling and distortion to occur easily, and cause making the result of heat-resisting dhering strength and the reduction of PCT peel strength on the contrary, thus not preferred.

Between the pairing sparking electrode of plasma electrode, apply the high frequency voltage of 800V～2000V, handle and implement high-frequency plasma (RF plasma).If the not enough 800V of this high frequency voltage then utilizes a little less than the processing excessively of plasma execution, can't show the rising of initial stage dhering strength; If surpass 2000V; Then, thereby cause when handling insulation film wrinkling and distortion to occur easily because processing can become by force, thus not preferred.

In addition, so-called " under the inert environments " is meant nitrogen, argon grade in an imperial examination 18 family's gases here, also can be the mist of nitrogen and argon.Particularly, just can make the PCT peel strength become more than 70% of initial stage peel strength if under nitrogen environment, utilize plasma to implement surface treatment.

Preferred 2 seconds～100 seconds of the processing time utilizing plasma discharge to implement.If the processing time deficiency of plasma discharge 2 seconds; A little less than then handling, cause not tool contribution of rising, handle if surpass 100 seconds lasting executions to the initial stage dhering strength; Then influence can be excessive; Cause insulation film that wrinkling and distortion takes place easily, the result that instead can cause heat-resisting dhering strength and PCT dhering strength to reduce, thereby not preferred.On the other hand, from productive viewpoint, the long process time that surpasses 100 seconds is not preferred yet.

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

When the single face of insulator film was implemented surface treatment, the oligomer amount of the insulator film after surface treatment was compared the preceding oligomer amount of surface treatment and is compared, preferably below 70%.Also have, when to the two-sided execution surface treatment of insulator film, the oligomer amount of the insulator film after surface treatment is compared with the oligomer amount before the surface treatment, is preferably below 35%.

The reason of utilizing this surface treatment to cause the oligomer amount to reduce is due to the oligomer cause that can be removed because of surface treatment.Here, so-called " oligomer " is the molecule of molecular weight 300～14000 scopes, when when making insulator film, fully do not carry out polymerization and can residue in the molecule in the film.The judgement of this oligomer amount is according to trying to achieve like following mensuration oligomer amount.From insulator film, use the oxolane equal solvent to extract oligomer, use size exclusion chromatography (SEC method) determining molecular weight to distribute this extract again and get final product.

1-3. substrate metal layer

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

If utilize that dry type plating method obtained by main be the bed thickness deficiency 5nm that adds the substrate metal layer that nickel-chromium alloy constitutes of element with chromium, even if via follow-up treatment step, the long-term adaptation of substrate metal layer still can go wrong.Also have, if the not enough 5nm of the bed thickness of substrate metal layer, then add the etching solution in man-hour and can infiltrate implementing distribution, situation such as cause taking place that wiring part floats, cause the obviously problem generation such as reductions of distribution peel strength, thus not preferred.

On the other hand,, then, can cause the difficulty of removing of substrate metal layer when the man-hour that adds of implementing wiring part if the bed thickness of substrate metal layer surpasses 50nm, and have take place that hair splits, warpage etc. and the situation that causes dhering strength to reduce, thereby not preferred.Also have, if bed thickness is to be thicker than 50nm, then because be difficult to implement etching, thereby still not preferred.

The one-tenth of this substrate metal layer is grouped into from thermal endurance and corrosion proof viewpoint, and the chromium ratio is necessary for 12 weight %～22 weight %.That is, if chromium ratio less than 12 weight % then can cause thermal endurance to reduce, on the other hand, if the chromium ratio surpasses 22 weight %, then add man-hour when implementing wiring part, removing of substrate metal layer becomes difficulty, thereby not preferred.And, in this nickel-chromium alloy,, can cooperate the purpose characteristic suitably to add transition metal in promoting under thermal endurance and the corrosion proof order.

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 the bed thickness of this substrate metal layer.

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

The chromium ratio is 4 weight %～22 weight %; Be for preventing that obviously reduction is necessary because of thermal degradation when causes heat-resisting peel strength, if the chromium ratio is lower than 4 weight %, even if then there is molybdenum to add; Can't prevent that still heat-resisting peel strength from obviously reducing because of thermal degradation when, thus not preferred.Also have, more than 22 weight %, then the etching meeting is tending towards difficulty, thereby not preferred as if the chromium ratio.Therefore, the situation of chromium, more preferably 4 weight %～15 weight %, special preferred 5 weight %～12 weight %.

Secondly, for asking the lifting of corrosion resistance, insulating reliability, the preferred 5 weight % of molybdenum ratio～40 weight %.If the molybdenum ratio is less than 5 weight %, then can not show additive effect, can't present the lifting of corrosion resistance, insulating reliability, thereby not preferred.Also have,, then have the extreme tendency that reduces of heat-resisting peel strength if the molybdenum ratio surpasses 40 weight %, thus not preferred.

Moreover the situation of usually Ni-based alloy target material is if the nickel ratio is greater than 93 weight %; Then sputtering target material itself just can become the ferromagnetism body, when utilizing magnetron sputtering to carry out film forming, can cause film forming speed to reduce; Thereby not preferred, and when utilizing sputter to form substrate metal layer of the present invention, because the target of sputter is formed below the nickel amount 93 weight %; Even if thereby when using magnetron sputtering method to carry out film forming, still can obtain good rate of film build.In addition, in this Ni-Cr-Mo alloy,, can cooperate the purpose characteristic and suitably add transition metal in promoting thermal endurance and corrosion proof purpose.

Moreover, in this substrate metal layer, except that Ni-Cr-Mo alloy, still can have the unavoidable impurities of being organized when making etc. below the 1 weight % that contains because of target.

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

1-4. insulator film (base material)

Moreover; In 2 layers of flexible substrate of the present invention, it is that film, polyamide-based film, ployester series film, polytetrafluoroethylene are that film, polyphenylene sulfide are that film, PEN are the resin film of selecting film, the polymerizable mesogenic system film that the insulator film of base material is preferably used from polyimides.

For example, the insulator film that is fit to thickness 25～75 μ m of use film.In addition, inanimate matter materials such as glass fiber because can become the obstacle of laser processing and chemical etching, thereby preferably do not use the substrate that contains inanimate matter material.

1-5. copper layer (conductor layer)

2 layers of flexible substrate of the present invention are after utilizing dry type plating method to form copper film layer on the substrate metal layer; On this copper film layer, utilize wet type plating method that copper wet type plating layer is set again, lamination is so that contain copper film layer and the thickness of copper wet type plating layer is that the copper layer of 10nm～12 μ m forms.

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

2 layers of flexible substrate of the present invention are if the surface is a copper film layer; Then the pinhole number of diameter 5 μ m～30 μ m being suppressed at per 1 square metre is below 45000; If the surface is a copper wet type plating layer; Then with diameter or greatest drawback length be the concave defect quantity of 10 μ m～20 μ m to be suppressed at per 1 square metre be below 2200, just applicable to the flexible wiring of making the thin space distribution.

2.2 the manufacturing approach of layer flexible substrate

Below, detail to the manufacturing approach of 2 layers of flexible substrate of the present invention.

Among the present invention; To being that film, polyamide-based film, ployester series film, polytetrafluoroethylene are that film, polyphenylene sulfide are that film, PEN are on the single or double of insulator film of the resin film selected film, the polymerizable mesogenic system film from polyimides as base material; Do not form substrate metal layer under the situation via bonding agent, and on this substrate metal layer, forming copper film layer.

The insulator film of base material normally contains moisture, must before the substrate metal layer that utilizes dry type plating method to form to be made up of nickel-chromium alloy, implement air drying or vacuumize, with the moisture removal that exists in the insulator film.Insufficient as if this is carried out, just can cause adaptation variation with substrate metal layer.

When utilizing dry type plating method to form substrate metal layer, when for example using the coiling type sputter equipment formation substrate metal layer of volume to volume (Roll to Roll), the target that just will have the substrate metal layer composition is installed in sputter with on the negative electrode.

At first; After implementing vacuum exhaust in the sputter equipment that insulator film is installed; Import the mist of nitrogen or argon or nitrogen and argon; And remain in will installing under the inert environments of pressure 0.8Pa～4.0Pa, apply 1500V～3000V direct voltage or 800V～2000V high frequency voltage between the pairing sparking electrode of article on plasma body electrode, and implement surface treatment at 2 seconds～100 seconds time utilization plasma.

Secondly; Import argon gas; Remain in about 1.3Pa in will installing, more on one side will be, the insulator film that lays out on the roller to be installed at the takers-in in the device, carry out conveyance with the speed about per minute 3m; Begin to carry out sputtering discharge from the sputter that negative electrode connected with direct current power supply electric power on one side, make the substrate metal layer that on insulator film, forms by nickel-chromium alloy or Ni-Cr-Mo alloy constituted.

The formation of copper film layer is same with the situation of substrate metal layer, uses and the copper target is installed in sputter with the sputter equipment on the negative electrode, with the copper film layer film forming.At this moment, substrate metal layer and copper film layer preferably form in same vacuum chamber continuously, after forming substrate metal layer, film are taken out in atmosphere, and when using other sputter equipments to form copper film layers, must implement dehydration fully in the past in advance in film forming.

Moreover, after utilizing dry type plating method to form copper film layer, when on copper film layer, utilizing wet type plating method to form copper wet type plating layer again, preferably implement for example electroless plating copper processing.This electroless plating applies and handles is through forming electroless plating copper layer at flexible substrate on the whole, even if the situation that has pin hole is arranged, still can cover this and expose face and make flexible substrate face integral body be good conductorization, just can suppressing to reduce the influence of pin hole thus.Wherein, when implementing the processing of electroless plating copper, must be careful the infiltration that is caused because of electroless plating deposited liquid and its pretreatment fluid and decide condition.

In addition; Utilize the bed thickness of the formed copper facing wet type of this non-cathode copper plating solution plating layer; But be if on the repairing substrate face because of defective that pin hole caused; And when implementing the electro-coppering plating solution and handling, the bed thickness of the degree that can not dissolve because of the electro-coppering plating solution gets final product the scope of preferred 0.01 μ m～1.0 μ m.

So form the substrate of electroless plating copper wet type plating layer; Be for forming the copper wet type plating layer of final required bed thickness; Handle and implement electro-coppering; The influence that just can obtain can not receive all size pin hole that produced when forming because of substrate metal layer to cause is good, and 2 layers of high flexible substrate of adaptation.In addition, be an all condition of taking according to the electrocoppering of well-established law execution as long as the electro-coppering of being implemented among the present invention is handled.

So the bed thickness of the copper wet type plating layer that forms on substrate metal layer and copper film layer had both made thick also preferably below 12 μ m.The reason that is made as like this bed thickness is for obtaining the distributing board of narrow distribution width, narrow wiring closet distance.

Whether in addition, on the surface of copper film layer, utilize wet type plating method to form copper wet type plating layer, be suitably to select according to the manufacturing approach of wiring part pattern.

For example, known when removing method and forming the wiring part pattern when utilizing, be utilize substrate metal layer, copper film layer, and copper wet type plating layer form wiring part, thereby must form copper wet type plating layer.To reach the desired bed thickness of wiring part.So-called " removing method " here; Be on the copper laminar surface of 2 layers of flexible substrate, resist layer to be set, the mask with set Wiring pattern is set on this resist layer again, quadrature is penetrated ultraviolet ray and is made public from it again; Through developing; To obtain to be used for unwanted copper layer etc. is carried out etched etching mask, the copper layer that then will expose is implemented etching and is removed the method for then more remaining resist layer being removed.Also be etched as the substrate metal layer in the unwanted place of wiring part and remove, and form the wiring part method of patterning.

On the other hand, when utilizing semi-additive process to form the wiring part pattern, also can on copper film groove, utilize wet type plating method that copper wet type plating layer is set, also can not be provided with.So-called " semi-additive process " here; Be meant on certain surface of metal level at 2 layers of flexible substrate (metal level that constitutes by substrate metal layer and copper film layer or the metal level that constitutes by substrate metal layer, copper film layer and copper wet type plating layer) resist layer is set; Mask with set Wiring pattern is set on this resist layer again, and quadrature is penetrated ultraviolet ray and is made public from it again, through developing; Just the plating that obtains to be used for electro-coppering on layer on surface of metal and form wiring part is used mask; The metal level that is exposed to peristome is used as negative electrode, forms wiring part through electroplating, then again resist layer is removed; Implement soft etching again and the unwanted 2 layers of flexible substrate surface metal except that wiring part are removed, form the wiring part method of patterning to accomplish wiring part.

[embodiment]

Below, utilize embodiment to specify the present invention, but the present invention is not limited to these embodiment.The mensuration of each characteristic be to use following shown in means implement.

The assay method of pin hole is with the substrate metal layer that utilizes dry type plating method to be obtained and the laminated body of copper film layer; The utilization mode of penetrating positions; Utilize its size of light microscope determining again, and the pin hole of mensuration diameter 5 μ m to 30 μ m is in per 1 square metre number.

The appraisal procedure of oligomer amount is to utilize oxolane to extract the insulation film after Cement Composite Treated by Plasma; Again extract is used size exclusion chromatography (SEC method); Measure the oligomer ratio of 380～13500 molecular weight; Numerical value before the Cement Composite Treated by Plasma is made as 100%, and compares and conduct " oligomer amount ".

The assay method of peel strength is to implement according to the method according to IPC-TM-650, NUMBER2.4.9, and as " initial stage peel strength ".Wherein, the wide 1mm that is made as of lead, peel angle is made as 90 °.Lead is to utilize the method that removes to form.Also have, stable on heating index is that the film substrate that forms 1mm lead film was positioned in 150 ℃ of baking boxs 168 hours, and after the taking-up, being placed to becomes till the room temperature, implement through assessing 90 ° of peel strengths, and as " heat-resisting peel strength ".

The index of moisture-proof is with the film substrate that forms 1mm lead film, in 121 ℃, 2 atmospheric press heaters, places 96 hours, and being placed to after the taking-up becomes till the room temperature, implement through assessing 90 ° of peel strengths, and as " PCT peel strength ".

The assay method of concave defect is surperficial to utilizing galvanoplastic to obtain copper wet type plating layer, uses light microscope to observe, and measures the size of concave defect.

When concave defect is circular situation; Measure per 1 square metre number of diameter 10 μ m to 20 μ m; When concave defect is except that the situation circular, then with the defective part length maximum of concave defect as " greatest drawback is grown ", measure per 1 square metre number of 10 μ m to 20 μ m concave defects.

(comparative example 1)

At first, comparative example 1 is to be presented at not implement the characteristic of implementing film formed 2 layers of flexible substrate under the Cement Composite Treated by Plasma situation.

In thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton150EN ") forms the 1st layer of substrate metal layer on the single face; The 1st layer of this substrate metal layer is to use 20 weight %Cr-Ni alloy target materials (Sumitomo Metal Mining Co., Ltd's system); In the Ar environment, utilize dc sputtering, with film forming speed 0.7nm/sec with 20 weight %Cr-Ni alloy substrates metal level film forming.According to the wherein part of the same terms film forming, (TEM: Hitachi Ltd.'s system) measure bed thickness, the result is 0.02 μ m to use transmission electron microscope in addition.On above-mentioned 20 weight %Cr-Ni films, further form the 2nd layer, the 2nd layer is to use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form the copper film layer of 100nm thickness, then utilizes till copper galvanoplastic film forming to the 8 μ m thickness again.

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

(embodiment 1)

Below, be illustrated in and implement the surface-treated situation of utilizing Cement Composite Treated by Plasma on the insulation film.

With thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton150EN ") be under the environment of 1.6Pa in nitrogen pressure; In between the pairing sparking electrode of plasma electrode, apply 50 seconds of 2000V direct voltage, only the substrate metal layer film forming face is implemented Cement Composite Treated by Plasma.Then; On plasma treated face, form the 1st layer of substrate metal layer at polyimides; The 1st layer of this substrate metal layer is to use 20 weight %Cr-Ni alloy target materials (Sumitomo Metal Mining Co., Ltd's system); In the Ar environment, utilize dc sputtering, with film forming speed 0.7nm/sec with 20 weight %Cr-Ni alloy substrates metal level film forming.

According to the wherein part of the same terms film forming, (TEM: Hitachi Ltd.'s system) measure bed thickness, the result is 0.02 μ m to use transmission electron microscope in addition.On this 20 weight %Ni-Cr film, further form the 2nd layer, the 2nd layer is to use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then utilizes copper galvanoplastic film forming to 8 μ m thickness again.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 624N/m, and the PCT peel strength is 434N/m, the dry type plating (laminated body of substrate metal layer and copper film layer.To call " dry type plating " in the following text) pinhole number be 36443/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 70%, the concave defect number is 1951/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 2)

With thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 2.4Pa; In between the pairing sparking electrode of plasma electrode, apply 50 seconds of 2000V direct voltage, only the substrate metal layer film forming face is implemented Cement Composite Treated by Plasma.Then; On plasma treated face, form the 1st layer of substrate metal layer at polyimides; The 1st layer of this substrate metal layer is to use 20 weight %Cr-Ni alloy target materials (Sumitomo Metal Mining Co., Ltd's system); In the Ar environment, utilize dc sputtering, with film forming speed 0.7nm/sec with 20 weight %Cr-Ni alloy substrates metal level film forming.According to the wherein part of the same terms film forming, (TEM: Hitachi Ltd.'s system) measure bed thickness, the result is 0.02 μ m to use transmission electron microscope in addition.On this 20 weight %Ni-Cr film, further form the 2nd layer, the 2nd layer is to use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then utilizes copper galvanoplastic film forming to 8 μ m thickness again.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 635N/m, and the PCT peel strength is 463N/m, and the pinhole number of dry type plating is 15571/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 56%, the concave defect number is 1645/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 3)

With thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 3.1Pa; In between the pairing sparking electrode of plasma electrode, apply 50 seconds of 2000V direct voltage, only the substrate metal layer film forming face is implemented Cement Composite Treated by Plasma.Then; On plasma treated face, form the 1st layer of substrate metal layer at polyimides; The 1st layer of this substrate metal layer is to use 20 weight %Cr-Ni alloy target materials (Sumitomo Metal Mining Co., Ltd's system); In the Ar environment, utilize dc sputtering, with film forming speed 0.7nm/sec with 20 weight %Cr-Ni alloy substrates metal level film forming.According to the wherein part of the same terms film forming, (TEM: Hitachi Ltd.'s system) measure bed thickness, the result is 0.02 μ m to use transmission electron microscope in addition.On above-mentioned 20 weight %Cr-Ni films, further form the 2nd layer, the 2nd layer is to use Cu target (Sumitomo Metal Mining Co., Ltd's system), utilizes sputtering method to form copper film layer 100nm thickness, then utilizes copper galvanoplastic film forming to 8 μ m thickness again.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 632N/m, and the PCT peel strength is 467N/m, and the pinhole number of dry type plating is 8236/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 50%, the concave defect number is 2005/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(comparative example 2)

Though desire is with thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton 150EN ") under the environment of nitrogen pressure 0.7Pa; In between the pairing sparking electrode of plasma electrode, apply 15 seconds of 500V direct voltage, but discharge is unstable, and can't handles.

(comparative example 3)

Though with thickness 38 μ m polyimide film (Dong Li E.I.Du Pont Company systems; Registered trade mark " Kapton150EN ") under the environment of nitrogen pressure 4.7Pa; In between the pairing sparking electrode of plasma electrode, apply 6 seconds of 3500V direct voltage and implement Cement Composite Treated by Plasma; But the surface has appearance wrinkling, causes follow-up characteristic evaluation to carry out.

(embodiment 4)

Remove and to be made as Ar Pressure 3.6Pa, and article on plasma body electrode apply direct current 2800V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 4 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 612N/m, and the pinhole number of dry type plating is 7428/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 50%, the concave defect number is 889/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 5)

Remove and to be made as Ar Pressure 1.6Pa, and article on plasma body electrode apply direct current 2200V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 5 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 627N/m, and the pinhole number of dry type plating is 5142/m ², and not having diameter to surpass the pin hole of 30 μ m, the oligomer amount is 70%.In addition, the concave defect of 2 layers of flexible substrate relating to of embodiment 5 is measured and is implemented.

(embodiment 6)

Remove and to be made as Ar Pressure 3.6Pa, and article on plasma body electrode apply direct current 1600V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 6 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 626N/m, and the pinhole number of dry type plating is 6428/m ², and not having diameter to surpass the pin hole of 30 μ m, the oligomer amount is 70%.In addition, the concave defect of 2 layers of flexible substrate relating to of embodiment 6 is measured and is implemented.

(comparative example 4)

Though be made as Ar Pressure 0.7Pa, and desire the direct current 500V that article on plasma body electrode applied for 6 seconds, it is unstable that discharge is, and can't handle.

(comparative example 5)

Though be made as Ar Pressure 4.7Pa, and article on plasma body electrode apply direct current 3500V and implement 6 second Cement Composite Treated by Plasma, the surface has and occurs wrinklingly, causes follow-up characteristic evaluation to carry out.

(embodiment 7)

Remove the mixed pressure 1.6Pa be made as 75 volume % argon-25 volume % nitrogen, and article on plasma body electrode apply direct current 1800V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 7 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 608N/m, and the pinhole number of dry type plating is 8571/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 70%, the concave defect number is 1855/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 8)

Remove the mixed pressure 1.6Pa be made as 75 volume % argon-25 volume % nitrogen, and article on plasma body electrode apply direct current 2300V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 8 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 599N/m, and the pinhole number of dry type plating is 7143/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 50%, the concave defect number is 1554/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 9)

Remove the mixed pressure 3.6Pa be made as 75 volume % argon-25 volume % nitrogen, and article on plasma body electrode apply direct current 1500V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 9 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 593N/m, and the pinhole number of dry type plating is 24000/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 60%, the concave defect number is 1762/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(comparative example 6)

Though be made as the mixed pressure 0.7Pa of 75 volume % argon-25 volume % nitrogen, and desire the direct current 500V that article on plasma body electrode applied for 6 seconds, it is unstable that discharge is, and can't handle.

(comparative example 7)

Though be made as the mixed pressure 4.7Pa of 75 volume % argon-25 volume % nitrogen, and article on plasma body electrode apply direct current 3500V and implement 6 second Cement Composite Treated by Plasma, the surface has and occurs wrinklingly, causes follow-up characteristic evaluation to carry out.

(embodiment 10)

Remove the mixed pressure 1.6Pa be made as 50 volume % argon-50 volume % nitrogen, and article on plasma body electrode apply direct current 3000V and implement 50 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 10 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 681N/m, and the pinhole number of dry type plating is 18276/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 70%, the concave defect number is 2076/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 11)

Remove the mixed pressure 1.6Pa be made as 50 volume % argon-50 volume % nitrogen, and article on plasma body electrode apply direct current 1800V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 11 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 572N/m, and the pinhole number of dry type plating is 15286/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 30%, the concave defect number is 1861/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 12)

Remove the mixed pressure 3.6Pa be made as 50 volume % argon-50 volume % nitrogen, and article on plasma body electrode apply direct current 2000V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 12 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 583N/m, and the pinhole number of dry type plating is 21286/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 40%, the concave defect number is 1889/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(comparative example 8)

Though be made as the mixed pressure 0.7Pa of 50 volume % argon-50 volume % nitrogen, and desire the direct current 500V that article on plasma body electrode applied for 6 seconds, it is unstable that discharge is, and can't handle.

(comparative example 9)

Though be made as the mixed pressure 4.7Pa of 50 volume % argon-50 volume % nitrogen, and article on plasma body electrode apply direct current 3500V and implement 6 second Cement Composite Treated by Plasma, the surface has and occurs wrinklingly, causes follow-up characteristic evaluation to carry out.

(embodiment 13)

Remove the mixed pressure 1.6Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply direct current 1600V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 13 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 586N/m, and the pinhole number of dry type plating is 8857/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 55%, the concave defect number is 1428/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 14)

Remove the mixed pressure 1.6Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply direct current 1800V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 14 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 567N/m, and the pinhole number of dry type plating is 11569/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 50%, the concave defect number is 1276/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 15)

Remove the mixed pressure 3.6Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply direct current 2000V and implement 6 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 15 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 584N/m, and the pinhole number of dry type plating is 22429/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 70%, the concave defect number is 1987/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(comparative example 10)

Though be made as the mixed pressure 0.7Pa of 25 volume % argon-75 volume % nitrogen, and desire the direct current 500V that article on plasma body electrode applied for 6 seconds, it is unstable that discharge is, and can't handle.

(comparative example 11)

Though be made as the mixed pressure 4.7Pa of 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply direct current 3500V and implement 6 second Cement Composite Treated by Plasma, the surface has and occurs wrinklingly, causes follow-up characteristic evaluation to carry out.

(embodiment 16)

Remove the mixed pressure 1.6Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 16 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 598N/m, and the pinhole number of dry type plating is 9847/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 65%, the concave defect number is 1564/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 17)

Remove the mixed pressure 1.6Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply high frequency 1000V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 17 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 608N/m, and the pinhole number of dry type plating is 15098/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 63%, the concave defect number is 2017/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 18)

Remove the mixed pressure 2.4Pa be made as 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 18 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 614N/m, and the pinhole number of dry type plating is 19713/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 70%, the concave defect number is 1798/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(comparative example 12)

Though be made as the mixed pressure 0.3Pa of 25 volume % argon-75 volume % nitrogen, and desire the high frequency 600V that article on plasma body electrode applied for 12 seconds, it is unstable that discharge is, and can't handle.

(comparative example 13)

Though be made as the mixed pressure 4.7Pa of 25 volume % argon-75 volume % nitrogen, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma, the surface has and occurs wrinklingly, causes follow-up characteristic evaluation to carry out.

(embodiment 19)

Remove and to be made as Ar Pressure 1.6Pa, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 19 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 598N/m, and the pinhole number of dry type plating is 25673/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 56%, the concave defect number is 1897/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 20)

Remove the mixed pressure 1.6Pa be made as 75 volume % argon-25 volume % nitrogen, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 20 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 587N/m, and the pinhole number of dry type plating is 19476/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 66%, the concave defect number is 1674/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 21)

Remove the mixed pressure 1.6Pa be made as 50 volume % argon-50 volume % nitrogen, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 21 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 569N/m, and the pinhole number of dry type plating is 24384/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 62%, the concave defect number is 1720/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

(embodiment 22)

Remove and to be made as nitrogen pressure 1.6Pa, and article on plasma body electrode apply high frequency 600V and implement 12 second Cement Composite Treated by Plasma outside, all the other all likewise make 2 layers of flexible substrate that embodiment 22 relates to embodiment 1.

The initial stage peel strength of 2 layers of flexible substrate that obtained is 601N/m, and the pinhole number of dry type plating is 27846/m ², and do not have diameter to surpass the pin hole of 30 μ m, and the oligomer amount is 59%, the concave defect number is 2008/m ², and do not have diameter or the long concave defect of greatest drawback above 20 μ m.

The result of the foregoing description, comparative example puts in order as shown in table 1.

Can know by table 1; Through insulator film is implemented the surface treatment according to the Cement Composite Treated by Plasma of institute of the present invention fixed condition; Can make the oligomer amount of insulator film become preceding below 70% of oligomer amount of surface treatment, and can the pinhole number of dry type plating be suppressed at 45000/m ²Below, and can the concave defect number of copper wet type plating layer be suppressed at 2200/m ²Down.

In addition, during the ambient pressure of surface-treated Cement Composite Treated by Plasma deficiency 0.8Pa, confirmed that discharge is unstable, and can't implement surface treatment insulator film.Have again, also learn for plasma electrode apply voltage if too high, then insulator film can occur wrinklingly, causes making 2 layers of flexible substrate.

Claims

1.2 layer flexible substrate, it is on the single face at least of insulator film, under the situation via bonding agent not, utilizes dry type plating method to form substrate metal layer, on this substrate metal layer, utilizes dry type plating method to form copper film layer; It is characterized by,

Above-mentioned insulator film is that one side is at least implemented surface treatment, only the one side of above-mentioned insulator film is implemented the oligomer amount after the above-mentioned surface treatment, is below 70% of oligomer amount before the surface treatment.

2. 2 layers of flexible substrate of claim 1 record, wherein, above-mentioned copper film layer has the thickness of 50nm～500nm, and does not have diameter to surpass the pin hole of 30 μ m, and diameter 5 μ m pin hole above and below the 30 μ m is per 1 square metre below 45000.

3. 2 layers of flexible substrate of claim 1 or 2 records wherein, utilize wet type plating method to form copper wet type plating layer on above-mentioned copper film layer.

4. 2 layers of flexible substrate of claim 3 record; Wherein, Above-mentioned copper wet type plating layer has the thickness of 0.5 μ m～12 μ m; And the concave defect that does not have the long 20 μ m of surpassing of diameter or greatest drawback, and diameter or the long 10 μ m of greatest drawback concave defect above and below the 20 μ m are per 1 square metre below 2200.

5. 2 of each record layers of flexible substrate in the claim 1 to 4; Wherein, Above-mentioned substrate metal layer has the bed thickness of 5nm～50nm; Form by containing nickel-chromium alloy, said nickel-chromium alloy is to be that main interpolation element 6 weight %～22 weight % surpluses are then constituted by nickel with chromium, and the bed thickness of the set conductor layer (copper layer) that is made up of copper film layer and copper wet type plating layer is 50nm～12 μ m on above-mentioned substrate metal layer.

6. 2 of each record layers of flexible substrate in the claim 1 to 5; Wherein, above-mentioned insulator film is to be that film, polyamide-based film, ployester series film, polytetrafluoroethylene are that film, polyphenylene sulfide are that film, PEN are the resin film of selecting film, the polymerizable mesogenic system film from polyimides.

7. 2 of each record layers of flexible substrate in the claim 1 to 6, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa～4.0Pa, the plasma discharge that utilizes 1500V～3000V direct voltage to be implemented on the surface of above-mentioned insulator film to handle.

8. 2 layers of flexible substrate of claim 7 record, wherein, above-mentioned surface-treated inert environments is a nitrogen environment, the PCT peel strength after the surface treatment is more than 70% of initial stage peel strength.

9. 2 of each record layers of flexible substrate in the claim 1 to 6, wherein, above-mentioned surface treatment is under the inert environments of pressure 0.8Pa～4.0Pa, the plasma discharge that utilizes 800V～2000V high frequency voltage is implemented on the surface of above-mentioned insulator film handled.

10. 2 layers of flexible substrate of claim 9 record, wherein, above-mentioned surface-treated inert environments is a nitrogen environment, the PCT peel strength after the surface treatment is more than 70% of initial stage peel strength.

11.2 the manufacturing approach of layer flexible substrate, it is on the single face at least of insulator film, under the situation via bonding agent not; Utilize dry type plating method to form substrate metal layer; On above-mentioned substrate metal layer, utilize dry type plating method to form copper film layer, it is characterized by

To the surface of above-mentioned insulator film under the inert environments of pressure 0.8Pa～4.0Pa, implement the surface treatment of the plasma discharge that applied for 2～100 seconds between the pairing sparking electrode that utilizes article on plasma body electrode after, form substrate metal layer.

12. the manufacturing approach of 2 layers of flexible substrate of claim 11 record, wherein, the above-mentioned surface treatment that utilizes plasma discharge is to apply 1500V～3000V direct voltage between the sparking electrode of article on plasma body electrode.

13. the manufacturing approach of 2 layers of flexible substrate of claim 11 record, wherein, the above-mentioned surface treatment that utilizes plasma discharge is to apply 800V～2000V high frequency voltage between the sparking electrode of article on plasma body electrode.

14.2 the manufacturing approach of layer flexible substrate; It is the manufacturing approach of 2 layers of flexible substrate of claim 8 record, is on the single face at least of insulator film, under the situation via bonding agent not; Utilize dry type plating method to form substrate metal layer; On above-mentioned substrate metal layer, utilize dry type plating method to 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; Execution forms substrate metal layer after utilizing the surface treatment of the plasma that applies 1500V～2～100 seconds of 3000V direct voltage between the pairing sparking electrode of article on plasma body electrode and produce.

15.2 the manufacturing approach of layer flexible substrate; It is the manufacturing approach of 2 layers of flexible substrate of claim 10 record, is on the single face at least of insulator film, under the situation via bonding agent not; Utilize dry type plating method to form substrate metal layer; On above-mentioned substrate metal layer, utilize dry type plating method to 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; Execution forms substrate metal layer after utilizing the surface treatment of the plasma that applies 800V～2～100 seconds of 2000V high frequency voltage between the pairing sparking electrode of article on plasma body electrode and produce.

16. the manufacturing approach of 2 of each record layers of flexible substrate in the claim 11 to 15, wherein, above-mentioned dry type plating method be vacuum vapour deposition, sputtering method, and the ion plating method in any.

17. the manufacturing approach of 2 of each record layers of flexible substrate in the claim 11 to 16; Wherein, above-mentioned insulator film is to be that film, polyamide-based film, ployester series film, polytetrafluoroethylene are that film, polyphenylene sulfide are that film, PEN are the resin film of selecting film, the polymerizable mesogenic system film from polyimides.