CN1934293B

CN1934293B - Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display using the surface-treated copper

Info

Publication number: CN1934293B
Application number: CN2005800064619A
Authority: CN
Inventors: 樋口勉
Original assignee: Mitsui Mining and Smelting Co Ltd
Current assignee: Mitsui Mining and Smelting Co Ltd
Priority date: 2004-03-02
Filing date: 2005-03-01
Publication date: 2010-04-21
Anticipated expiration: 2025-03-01
Also published as: TW200533251A; TWI280079B; KR20070004658A; WO2005083157A1; CN1934293A; JP4458521B2; JP2005248221A; KR100869196B1

Abstract

A surface-treated copper foil that exhibits an excellent gray and can be worked by the common copper etching process; and an electromagnetic wave shielding conductive mesh for PDP produced with the use of the surface-treated copper foil. There is provided, for example, a surface-treated copper foil furnished on its one major surface side with a surface having undergone graying treatment, characterized in that the surface having undergone graying treatment results from formation of a cobalt sulfate plating layer on a rough surface of copper foil layer and further formation of a layer treated for corrosion prevention. Moreover, there is provided, for example, a process for producing the surface-treated copper foil, comprising electrolyzing a cobalt plating solution containing cobalt sulfate (heptahydrate) at a given current density onto a rough surface of electrolytic copper foil, etc. to thereby form a layer treated for corrosion prevention and performing water washing and drying thereof.

Description

Possess the manufacture method of surface treatment copper foil, this surface treatment copper foil of grey treated side and the electromagnetic wave shielding conductive mesh that has used the front panel of the plasma display of this surface treatment copper foil to use

Technical field

The present invention relates to a kind of electromagnetic wave shielding wire cloth that possesses the surface treatment copper foil of grey treated side and used the front panel of the plasma display of this surface treatment copper foil to use.The surface treatment copper foil of the manufacturing of the electromagnetic wave shielding conductive mesh that a kind of front panel that is suitable for plasma display uses particularly, is provided.

Background technology

The shielding conductive mesh of plasma display device forms to the conductive mesh variation from the metalized fibers fabric.At the manufacture view of this conductive mesh, there is certain methods to establish.One of them is method surface treatment copper foil is stacked and that be bonded on the PET film, use photoetching method to make.In addition, another kind be utilize photoetching method with surface treatment copper foil with the supporting substrate etching, peel the monomeric conductive mesh of surface treatment copper foil of supporting substrate off thereafter.

Especially, in recent years, according to the requirement of saving electric power, fade to 50V from 200V and carry out plasma is produced signal voltage as the exploitation of target, follow this voltage to descend and the minimizing of brightness, attempting circuit width graph thinning, reducing the lining rate of the front glass panel that causes by conductive mesh conductive mesh.Therefore, make the thickness attenuation of conductive mesh, also carrying out with the work that is easier to etching and processing.One of them is initial (seed) layer that becomes plating seed by the sputter vapour deposition method on the PET film, utilizes mode such as electrolytic copper plating to form thin copper layer thereafter, utilizes photoetching method then, make the miniaturization of web lines width the manufacturing of conductive mesh.

No matter make conductive mesh with which method in these methods, conductive mesh itself is to be assembled into also to see through the member that front glass can be recognized from the surface in the front panel, and those skilled in the art uses the surface treatment copper foil that possesses black treat surface or dark brown treat surface always.(the existing surface treatment copper foil that possesses the black treat surface)

The single face that is processed into the surface treatment copper foil of this conductive mesh is treated to black, to improve the brightness that sees through light.All the time, in this is handled, migrate gradually and handle for the melanism that improves formation copper oxide multilayer printed circuit board, that carry out with the connectivity of the resin layer of internal layer circuit.

But, in above-mentioned melanism is handled, have great problem.That is,, then can obtain good black face really if be attached with the black oxide of a lot of copper at copper foil surface.But the black oxide adhesion amount of copper that is formed on copper foil surface is many more, falls from the black emaciated face just easily more, thereby causes so-called dry linting phenomenon, causes the melanism treated side to sustain damage intractable easily.In addition, the problem that also has the stability of the tone of black to lack.

The powder phenomenon in case fall, the black oxide that then comes off can be blended into useless place, perhaps making when handling with the incorporate transparence of the glass of front panel, is distributed in the translucent adhesive layer, becomes the major cause that transparency is worsened.

On the other hand, as the black processing that can form good black face, once study general black nickel plating, nickelous sulfide plating, cobalt plating etc., but in common copper etching technique, produced the problem that to carry out etching and processing from black treated side side.Particularly, have the surface treatment copper foil of the black treated side of having separated out cobalt or nickel in a large number, not only can not solve the problem of dry linting, owing to used a large amount of high price nickel etc., and become high priced line.

(the existing surface treatment copper foil that possesses the dark brown treat surface)

On the other hand, the manufacturing technology of plasma display device is very ripe, only require surface treatment copper foil with good black face all the time, and along with the High Level of manufacturing technology and management, there is no need the black concentration requirement of electromagnetic wave shielding silk screen very high, but wish that low price is arranged, and etching and processing is easy, has the electromagnetic wave shielding silk screen of the silk-screen patterns of the stable high aperture of the transmitance of light.

Therefore, possessing of circulating on the present market black system of cobalt electroplate on the Copper Foil of tunicle, produce owing to use the etching reagent of copper to cause being difficult to carrying out the problem of the etching and processing of cobalt layer, and begin to attempt reducing the amount of dissimilar metal and the Copper Foil of making the dark brown tone.

Really, if consider to satisfy condition and easy etched words at a low price, then study adhesion amount before the surface of surface treatment copper foil reaches blackization, that reduce cobalt etc. and the umbrinaceous state that forms is supplied to market always.

But the irregular colour that existing shortcoming with the surface treatment copper foil on umbrinaceous surface is this dark brown face is even, produces irregular on whole surface.That is, can not make the umbrinaceous processing homogenizing in same, the cross-sectional shape that becomes the silk screen that obtains by etching produces inhomogenous reason.And this dark brown face only just is easy to sustain damage by its surface that rubs lightly.

Therefore, on market, wish to have a kind of surface treatment copper foil that has even umbrinaceous dark brown processing layer and can more easily carry out etching and processing.

And, possess the above-mentioned black treated side and the Copper Foil of dark brown treated side, the problem that all has tone stability, and, irregular between dwindling batch, the management of need creating conditions closely needs very big supervision of construction labour and expense, thus reducing product price to having produced certain restriction aspect the market supply.Be generally considered to be related prior art following document is arranged.

The technology trend Hitachi forming technology report (Hitachi changes into テ Network ニカ Le レ Port one ト) No. 33 (1999-7) of non-patent literature 1:PDP material.

Patent documentation 1:JP spy opens flat 11-186785 communique.

Disclosure of an invention

The problem that invention will solve

But, the Copper Foil that what is called possesses above-mentioned black treated side and dark brown treated side is to confirm that with state that can enough Copper Foils tone is a problem, the tone when not considering to be processed as electromagnetic wave shielding conductive mesh and being assembled into the front panel of plasma display.

At this, sketch the manufacture method of prevailing front strainer.Making spacing is 200 μ m, live width when being conductive mesh 15 below the 20 μ m, is ready to the PET film F like that shown in Figure 14 (a), becomes the state shown in Figure 14 (b) by adhesive layer 20 is set on its surface.Then, shown in Figure 14 (c),, thereafter, shown in Figure 14 (d), form the copper layer C of the following degree of 3 μ m by the electrolytic copper plating at the metal initial layers S that uses sputtering method (sputtering), plated by electroless plating method to wait on the adhesive layer 20 to form below the 1 μ m.

Then, on this copper layer C, shown in Figure 14 (e), form resist layer R, at this resist layer R, shown in Figure 15 (f), the conductive mesh pattern P is exposed, and shown in Figure 15 (g), develop, become the state shown in Figure 15 (h) by etching then, become state shown in Figure 15 (i) by peeling off resist layer R.

Then, carry out the black processing, shown in Figure 15 (j), become the state that has formed black processing layer 17 on the surface of conductive mesh by surface to conductive mesh 15.Then, after this black processing finishes, shown in Figure 16 (k), by the first transparency carrier 19a that constitutes the front strainer being contacted with the conductive mesh 5 ' of finishing the black processing and pressurizeing, shown in Figure 16 (1), be pressed into the conductive mesh 15 ' of finishing the black processing in the adhesive layer 20 and carry out transparence and handle.Then, shown in Figure 16 (m), peel off the PET film.Shown in Figure 16 (n), the adhesive layer 20 and the second transparency carrier 19b are bonded together at last, finish front strainer 11.

From above-mentioned operation as can be known, cannot see even before transparence is handled, carry out blackization or dark brownization, as long as after transparence is handled, with transparent resin or transparency carrier bonding state under conductive mesh surface blackization and can recognizing get final product.

In the long run, estimate that earthwave is with digitizing, the high speed of the transfer rate of picture signal also is inevitable, consider to give influence that human body and other electronicss bring etc., can imagine that the method regulation that obtains electromagnetic shielding also will be reinforced, the requirement of the good front strainer of electromagnetic wave shielding is also higher for using conductive mesh, requires cheap and high-quality conductive mesh.

The means that are used to deal with problems

At this, the result of the present inventor etc. further investigation has expected that the surface treatment copper foil that following use possesses the grey treated side makes the scheme of electromagnetic wave shielding with conductive mesh.By using this to possess the surface treatment copper foil of grey treated side, before transparence in the manufacturing process of the front of plasma display device strainer is handled, electromagnetic wave shielding is gray with the tone of conductive filament net surface, after transparence was handled, electromagnetic wave shielding can be recognized with the conductive mesh surface blackization.

＜possess the surface treatment copper foil of grey treated side 〉

The surface treatment copper foil that possesses the grey treated side that the present invention relates to comprises situation that does not possess antirust processing layer and the situation that possesses antirust processing layer.Though therefore antirust processing layer not necessarily becomes necessary formation as surface treatment copper foil in order to ensure prolonged preservation.The surface treatment copper foil that the present invention relates to below is described.

First surface is handled Copper Foil:The surface treatment copper foil that the present invention relates to, be that " surface treatment copper foil (hereinafter referred to as " first surface processing Copper Foil ") that possesses the grey treated side on the uneven surface of electrolytic copper foil; it is characterized in that, this grey treated side are that the gravimetric thickness in the single face setting of copper foil layer is 200mg/m ²～350mg/m ²The rose vitriol electrolytic coating, and the cross-sectional height of this grey treated side is below the 200nm.Fig. 1 has represented that schematically the cross-sectional layers of this surface treatment copper foil 1a constitutes.

In this Fig. 1, schematically put down in writing the surface treatment copper foil 1a that on the uneven surface of electrolytic copper foil 7, forms rose vitriol electrolytic coating 4 and implemented the state of roughening treatment at the fine shot copper 3 of opposing face (suitable under the situation at electrolytic copper foil) use with glossy surface as an example.But whether the opposing face of the Copper Foil of Shi Yonging carries out roughening treatment all it doesn't matter at this moment.At this, in Fig. 2, schematically the expression omitted opposing face roughening treatment the time surface treatment copper foil 1b.The roughening treatment layer 2 that constitutes with fine shot copper 3 with improve with the cohesiveness of base material etc. etc. be that purpose forms, can be provided with as required.Form the method for this roughening treatment layer 2, can adopt the method for aforesaidly adhering to the method that forms fine shot copper, fine cupric oxide being adhered to etc., coarsing processing method is not limited especially.

Then, in this copper foil layer 7, have on the surface of certain convexo-concave roughening rose vitriol electrolytic coating 4 is set.At this as roughness that uneven surface had, with nominal thickness be that the suitable roughness of the uneven surface of electrolytic copper foil of the thickness below the 35 μ m is only, the mean roughness (Ra) that the probe-type roughmeter that preferably is in radius-of-curvature with probe front portion and is 2 μ m is surveyed periodic JIS-B-0601 defined is that 1.0 μ m are following, 10 mean roughness (Rz) are in the following scope of 4.0 μ m.When more coarse than this roughness, the grey change the tone deficient in stability of surface treatment copper foil, carry out etching and etching precision when being processed into the silk screen shape worsens, thereby have the tendency of high-quality electromagnetic wave shielding with the fabrication yield variation of conductive mesh.And more preferably mean roughness (Ra) is below the 0.5 μ m, and 10 mean roughness (Rz) are below the 2.8 μ m.The stability of the gray tone of surface treatment copper foil significantly improves, and in the front panel manufacturing process of plasma display device, the irregular of tone of the black after transparence is handled tails off.

The meaning at this said rose vitriol electrolytic coating 4 is to use the layer of cobalt sulfate solution by electrochemical plating formation.And this rose vitriol electrolytic coating 4 can be recognized as grey under the state of surface treatment copper foil.But, in the front panel manufacturing process of above-mentioned plasma display device, carry out transparence and handle, become on the grey treat surface after the state that is covered by resin film or resin glue etc., can recognize as black.Tonal variation can obtain and following identical effect in this wise: if with the clothes water-wet of dark color, then should form water curtain for the clothing surface of coarse state former, thereby form slick surface, suppressed the diffuse-reflectance of the light that received thus, can recognize as darker color.

This rose vitriol electrolytic coating 4 is to be 200mg/m by adopting manufacture method described later to form gravimetric thickness ²～350mg/m ²The rose vitriol electrolytic coating, can form thus relative copper etchant solution the solvability excellence and the grey change the surface.Existing cobalt layer with Copper Foil of the black system plating tunicle that has used the cobalt layer, its gravimetric thickness is 1000mg/m ²About, very thick, different aspect this quality of solvability of coating.Consequently, so slack-off because have the dissolution rate of thickness copper etchant solution, simultaneously, become cobalt element this accumulates and makes the major cause of the usefulness reduction of etching solution in copper etchant solution middle and high concentration ground.In addition, converted weight of the present invention is the value that is scaled weight of cobalt.Converted weight is that surface treatment copper foil is dissolved in the acid solution, utilizes plasma luminescence spectrum analysis method etc. to try to achieve the cobalt contents of unit surface, is scaled the weight of every square metre of surface treatment copper foil again.

In addition, whether the cobalt electrolytic coating is easy to be dissolved in the copper etchant solution as can be known, can be subjected to very big influence according to carrying out the plating condition of cobalt when electroplating.That is it is etching characteristic the best that the cobalt that, has been obtained when having adopted the manufacture method of the following surface treatment copper foil that the present invention relates to is electroplated tunicle.

The surface shape that second characteristic that surface treatment copper foil had that the present invention relates to are these grey treated sides is not an extremely rough, and the cross-sectional height that this grey treated side is had is below the 200nm, and this is very large feature.That is, can make extremely sliding grey treated side.But clear and definite record is in order not allow the people misread, in the scope of common manufacturing process, there be irregular being inevitable, there is no need to allow the cross-sectional height all be below the 200nm in all positions, reflecting under the inhomogenous degree of manufacturing process, existing the situation of the cross-sectional height that surpasses 200mm also to be inevitable.For the cross-sectional height of the rose vitriol electrolytic coating 4 of measuring the surface treatment copper foil 1 that the present invention relates to, the FIB that uses the FIB analytical equipment to observe the cross section observes image as shown in Figure 3.In this Fig. 3, be illustrated in the material that has formed the grey treated side on the glossy surface of electrolytic copper foil.In addition, this FIB observation image is from become the direction at 60 ° of angles observable with respect to observed surface.

As can be seen from Figure 3, obviously the cross section of grey treated side exist certain concavo-convex, this when concavo-convex in monitoring, generally use the surfaceness meter of probe-type.But, according to the scale of Fig. 3 as can be known, have the concavo-convex of the degree that can't correctly measure with the surfaceness meter.At this, in the present invention, as with the periodic Rmax of surfaceness instrumentation corresponding value, FIB observes crest portion in the visual field of image and the maximum difference between the trough portion as " cross-sectional height ".Place by " d " expression in this Fig. 3 becomes the cross-sectional height of Fig. 3 and can be judged as about 80nm.And, in Fig. 3, rose vitriol electrolytic coating 4 forms with the shape of utmost point homogeneous thickness along copper foil surface, and keeps the state of fitting fully with the copper foil surface of substrate, can't see rose vitriol electrolytic coating 4 and bad place such as float, also can't see the place that dry linting can take place premonition.

Relative therewith, carry out FIB according to the cross section same as described abovely and observe the existing black treated side that on copper foil surface, forms, obtain Fig. 4 and result as shown in Figure 5.That is, the shape that constitutes the black treated side is dendroid grows up, and becomes from the quite outstanding state of the Copper Foil of substrate.Therefore,, then be about 480nm under the situation of Fig. 4, for about 270nm, become very coarse surface under the situation of Fig. 5 if measure the cross-sectional height (d) of this moment.And, we can say that this black treated side with branch shape is that its dendroid portion fractures and the surface of easy damage easily, if and the part that fractures comes off, it also is nature that dry linting takes place so, causes from the reason of black treat surface with visual being seen uneven color thereby become.

The above-mentioned surface treatment copper foil that the present invention relates to, the surface that has dead smooth as can be known according to FIB cross-section image from Fig. 3.And the L value in the Lab color specification system of this grey treated side is below 43.At this, as being recited as below 43, the upper limit is limited especially, but about 38 be lower limit rule of thumb.

The grey treated side of the surface treatment copper foil that the present invention relates in addition, has certain gloss and preferably adopts glossiness to represent gloss intensity.The glossiness of the grey treated side that the present invention relates to is that glossiness [Gs (60 °)] is below 10 in the result that the uneven surface of electrolytic copper foil has formed this grey treated side preferably.If glossiness is more than 10, then so-called metalluster becomes showy.In addition, at this, though the lower value of glossiness is not fixed, rule of thumb about 0.5 is lower limit.More preferably, glossiness is in 0.5～3.0 scope.Gray tone under the situation of glossiness in this scope stable best.

The grey treated side of above-mentioned surface treatment copper foil is adjacent to when having disposed the transparent resin tunicle on its surface, can recognize as black.Black concentration during the grey treated side of direct viewing this moment is 0.7～1.2 (condition determination: state T, sampling point 1.5 * 2mm, no polarizing filter), if be adjacent to configuration transparent resin tunicle on the surface of this grey treated side, then black concentration is (to be limited to about 1.8 rule of thumb) more than 1.4.All the time, the black concentration of the black treated side of the employed surface treatment copper foil of electromagnetic wave shielding silk screen of plasma display device, black concentration when direct viewing black treated side is about (result of the products measure that can obtain in the usefulness market such as inventor is 1.30～1.67) more than 1.0, if be adjacent to configuration transparent resin tunicle on the surface of this black treated side, then black concentration is (result of the products measure that can obtain in the usefulness market such as the inventor is 1.40～1.87) more than 1.5.Thus, use the surface treatment copper foil with grey treated side that the present invention relates to, if be adjacent to configuration transparent resin tunicle on this surface, black concentration is more than 1.4, then we can say black concentration abundance.In addition, the black concentration among the present invention is based on JIS B 9620, JIS B 9622 and measures, and adopts the said determination condition.

Second surface is handled Copper Foil:This surface treatment copper foil is the surface treatment copper foil that is formed for guaranteeing the antirust processing layer of prolonged preservation on above-mentioned first surface is handled the surface of Copper Foil.Fig. 6 schematically illustration possess the cross-sectional layers structure of the surface treatment copper foil 1c of antirust processing layer 5 on the two sides.And, represented that at Fig. 7 single face has omitted the surface treatment copper foil 1d under the situation of roughening treatment.As Copper Foil only is being in the purpose scope with antirust, can the widespread use imidazoles, organic rust preventing such as benzotriazole and by the zinc alloy of general zinc that adopts or brass etc. realize inorganic antirust etc.In addition, formed the antirust processing layer under the situation of rose vitriol electrolytic coating at single face, should in the surface treatment copper foil that the present invention relates to, be provided with the opposing face setting of rose vitriol electrolytic coating at least, even but be provided with on the two sides and also do not have what obstruction.

But; if antirust processing layer 5 is set on its two sides; then these antirust processing layers performance prevent roughening treatment layer 2 fine shot copper 3 come off and effect as the protective layer of rose vitriol electrolytic coating 4 in, also play the effect of keeping for a long time as the outward appearance of surface treatment copper foil.Particularly preferably in this antirust processing layer 5 zinc-nickel alloy or zinc-cobalt layer are set.These antirust processing layers 5 are by being used in combination with rose vitriol electrolytic coating 4, can play when making rose vitriol electrolytic coating 4 etchings dissolving the effect as dissoluting cocatalyst.That is, than the situation of rose vitriol electrolytic coating 4 Individual existences, if possess zinc-nickel alloy or zinc-cobalt layer, then the dissolving of rose vitriol electrolytic coating 4 can promptly be carried out.

Further, schematically represented to possess the cross-sectional layers structure of the surface treatment copper foil 1c that antirust processing layer 5 and chromate treating layer 6 are arranged on the two sides at Fig. 8 and Fig. 9.Respectively comparison diagram 6 and Fig. 8, Fig. 7 and Fig. 9 are only possessing chromate treating layer 6 this point with the difference of the surface treatment copper foil that possesses antirust processing layer 5 as can be known, and other structure is identical.

This chromate treating layer 6 is after having formed by zinc-nickel alloy or antirust processing layer 5 that zinc-cobalt layer etc. constitutes, forms on single face or two sides.And, utilize the existence of this chromate treating layer 6, the antioxidant property of surface treatment copper foil can be improved significantly, thereby surface corrosions (cosmetic corrosion) such as oxidation stain can be prevented effectively.

＜possess the manufacture method of the surface treatment copper foil of grey treat surface 〉

The manufacture method that the manufacture method of Copper Foil (first surface handle) above-mentioned first surface is handled Copper Foil preferably adopts the manufacture method that comprises following such operation.The prerequisite of this manufacture method is to adopt to stir to bathe.

The Copper Foil that uses in the manufacture method of the surface treatment copper foil that the present invention relates to is not limited to and above-mentionedly whether has carried out roughening treatment like that on the opposing face that forms the rose vitriol electrolytic coating.For clear and definite and under the record earlier, do not have special qualification at this, for example, under the situation that forms this atomic thin shot copper, in general can use the copper electrolyte that contains arsenic for the condition of the situation of implementing roughening treatment.For example, in copper sulfate class solution, condition is that copper concentration is that 5～10g/L, sulfuric acid concentration are that 100～120g/L, cl concn are that 20～30ppm, 9-phenylacridine are that 50～300mg/L, fluid temperature are 30～40 ℃, current density 5～20A/dm ²Deng.

In a) operation, on the uneven surface of above-mentioned Copper Foil, use that the rose vitriol (7 hydrate), the pH value that comprise 10g/L～40g/L are 4.0 or more, fluid temperature be rose vitriol electroplate liquid below 30 ℃ as the stirring bath, use 4A/dm ²Following current density is carried out electrolysis, forms gray rose vitriol electrolytic coating.That is, at this, the different of essence of handling the manufacture method A of Copper Foil with first surface are, carry out the electrolysis this point when carrying out stirring above-mentioned rose vitriol electroplate liquid when rose vitriol is electroplated.About this cobalt sulfate concentration, there is the low more tendency that just might make good grey state more of cobalt sulfate concentration.But, rose vitriol in the rose vitriol electroplate liquid (7 hydrate) then adopts the electroplating velocity that stirs the rose vitriol electrolytic coating of bathing formation slack-off if do not reach 10g/L, and, the tendency grow in uneven thickness of sulfuric acid nickel dam, thus cause being short of the result of industrial production.Relative therewith, if rose vitriol (7 hydrate) surpasses 40g/L, then formed rose vitriol electrolytic coating is difficult to form fine and close concavo-convex, consequently good gray states disappearance.

In addition, the pH value of the solution of the rose vitriol electroplate liquid of preferred this moment is that target is adjusted with the scope more than 4.0.And, more preferably 4.5～5.5 scope.In this scope, the yield rate height can obtain good grey cobalt electrolytic coating.As the operation of adjusting this pH value, other ionogen such as interpolation sodium hydroxide or potassium hydroxide is unfavorable.In the grey of cobalt coating, add metallic color easily.

Therefore, by the solution metal ionic concn is maintained necessarily, the pH value stabilization that as a result of makes solution is in the scope more than 4.0.Like this in order to make the concentration of cobalt ions in the solution stable, the following gimmick of preferred employing: use deliquescent cobalt electrode that galvanized cobalt ion dissolving is supplied with, perhaps monitor concentration of metal ions continuously and use cobaltous hydroxide suitably to add, stablize the concentration of cobalt ion thus.

And the fluid temperature of the rose vitriol electroplate liquid of preferred this moment is below 30 ℃.The low more tendency that can access good grey treated side more of fluid temperature that has this moment.If fluid temperature is set at below 30 ℃, then can obtain to be better than having implemented the good grey treated side of black processing at the copper foil surface that does not carry out roughening treatment with the manufacture method A of above-mentioned first surface processing Copper Foil.

The stirring of this moment, the flow velocity of the result's who has preferably stirred solution is in the scope of 20cm/s～40cm/s.When the flow velocity of solution does not reach 20cm/s, in above-mentioned solution composition, the ion of the plating face of electroplating cobalt is supplied with slack-off, it is elongated to electroplate the required time, and the tone of the grey treat surface that is obtained generation is irregular easily.On the other hand, when the flow velocity of solution surpasses 40cm/s, become excessive by stirring the ion feed speed that produces, the grey treat surface becomes near black, and metalluster strengthens, thereby can not obtain the grey treat surface that purpose of the present invention will obtain.

Current density when carrying out electrolysis is used 4A/dm ²Following electric current.In this scope,, also can form good rose vitriol electrolytic coating with micro concavo-convex with organic materials stickiness excellence even copper foil surface is not carried out roughening treatment.Usually, in order to obtain the plate surface of irregular black class, adopt the superfluous method of burning the Faradaic current in plating zone that enters that passes to.But, be used for more little, the stable and good possible more tendency of grey processing of electrolytic current density in this existence.Therefore, though adopt little current density good as much as possible, if consider the productivity of industry then can judge with current density 0.5A/dm ²As lower value.On the other hand, in case current density surpasses 4A/dm ², then have the tendency that obtains near the tone of black processing, thereby lost the meaning that adopts this manufacture method.And the grey treat surface that forms in the scope of above-mentioned current density can not occur from this dry linting phenomenon.

At b) in the operation, to the Copper Foil through above-mentioned operation wash, drying, be the surface treatment copper foil of grey treated side thereby obtain to make the rose vitriol electrolytic coating.At this method for washing, drying means are not limited especially, can adopt common thinkable mode.

(second surface is handled the manufacture method of Copper Foil)

Handle at second surface under the situation of Copper Foil, the manufacture method of handling Copper Foil with above-mentioned first surface is identical, makes the surface treatment copper foil of rose vitriol electrolytic coating as the grey treated side, thereafter, carries out the formation of antirust processing layer.Therefore, manufacturing process is: " a) form gray rose vitriol electrolytic coating on the glossy surface of Copper Foil.B) two sides or the single face at the Copper Foil that has formed gray rose vitriol electrolytic coating forms antirust processing layer.C) wash thereafter, drying ".That is, only in the manufacture method of first surface processing Copper Foil, increased the formation operation of antirust processing layer.

Therefore, at this content relevant with the formation operation of antirust processing layer only is described.The two sides or the single face of the Copper Foil of having finished in the formation of gray rose vitriol electrolytic coating form antirust processing layer.About inorganic antirust etc. the situation of using organic rust preventing such as present known imidazoles, benzotriazole and realizing by the zinc alloy of general zinc that adopts or brass etc., do not need to specify, as long as do, so omit detailed explanation at this according to usual method.

Below, illustrate about using zinc nickel alloy electroplating liquid or zinc-cobalt alloy electroplate liquid to carry out the situation that electroplating processes forms antirust processing layer.At first, zinc-nickel alloy is described.Though do not stipulate employed zinc nickel alloy electroplating liquid is special at this, but give one example at this, the employing condition is: the nickel concentration that uses single nickel salt is that 1～2.5g/L, the zinc concentration that uses zinc pyrophosphate are that 0.1～1g/L, potassium pyrophosphate are that 50～500g/L, fluid temperature are that 20～50 ℃, pH value are 8～11, current density is 0.3～10A/dm ²Deng.

Then, the zinc-cobalt alloy plating is described.Though do not stipulate employed zinc-cobalt alloy electroplate liquid is special at this, but give one example at this, the employing condition is: the cobalt concentration that uses rose vitriol is that 1～2.5g/L, the zinc concentration that uses zinc pyrophosphate are that 0.1～1g/L, potassium pyrophosphate are that 50～500g/L, fluid temperature are that 20～50 ℃, pH value are 8～11, current density 0.3～10A/dm ²Deng.Made up that this zinc-cobalt alloy is electroplated and the antirust processing layer of following chromate treating, demonstrated outstanding especially etch resistant properties.

Handle at second surface under the situation of Copper Foil, after the surface of Copper Foil has formed zinc-nickel alloy layer or zinc-cobalt alloy layer etc.,, just can obtain better erosion resistance if form chromate coating.That is, after having formed above-mentioned antirust processing layer, as long as the chromate treating operation is set.In this chromate treating operation, in making chromatedsolution and replacement Treatment that this copper foil surface contacts, can adopt and in chromatedsolution, carry out electrolysis and form any one method that the electrolytic chromate of chromic salt tunicle is handled.In addition, about chromatedsolution as used herein, can use the material of the scope that is adopted usually.And, thereafter, by the surface treatment copper foil of washing, drying obtains to possess the grey treated side.

＜electromagnetic wave shielding conductive mesh〉the above-mentioned surface treatment copper foil that possesses the grey treated side that the present invention relates to, can be from dry linting on the grey treated side, and have the good gray while, this grey processing layer can be removed in enough common copper etching technique etchings.Therefore, use the technology of making printed circuit board (PCB) can easily be processed as arbitrary shape.Consider these, we can say the electromagnetic wave shielding conductive mesh on the front panel that is suitable for being assembled into plasma display device most.

The effect of invention

The surface treatment copper foil that possesses the grey treated side that the present invention relates to even the rose vitriol electrolytic coating is very thin, also presents the good grey of the electromagnetic wave shielding conductive mesh of the front panel that is fit to plasma display device.And,, so etching is good, and can not reduce the effectiveness of the copper etchant solution of common iron(ic) chloride, sulfuric acid-hydroperoxide kind, thereby can make the solution life-span long-term because cobalt contents is few.

In addition, the manufacture method of the surface treatment copper foil that the present invention relates to can be made above-mentioned surface treatment copper foil under the state of high rate of finished products, and adopts the above-mentioned rose vitriol electrolytic coating that forms of creating conditions to be dissolved in the copper etchant solution efficiently.

The best mode that carries out an invention

The above-mentioned surface treatment copper foil that possesses the grey treated side is made in expression below, and uses copper etchant solution to make the result of electromagnetic wave shielding conductive mesh.

Embodiment 1

In the present embodiment, make first surface shown in Figure 1 and handle Copper Foil 1a, tentatively make the electromagnetic wave shielding conductive mesh shape and confirmed etching performance with etching method.

In the present embodiment, having used the nominal thickness that obtains by the electrolysis copper-bath is the Copper Foil of 15 μ m.Then, using sulfuric acid concentration is 30 ℃ dilution heat of sulfuric acid as 150g/L, fluid temperature, Copper Foil is immersed in this solution 30 seconds carries out cleaning of surface.

And, be that the glossy surface of the electrolytic copper foil of 15 μ m has been implemented roughening treatment to nominal thickness.The roughening treatment of this moment, be that this fine shot copper 3 is adhered on the single face that is formed on Copper Foil 7, the electrolytic condition that adopts is: copper sulfate class solution, wherein concentration is that copper 10g/L, sulfuric acid 100g/L, chlorine 25ppm, 9-phenylacridine are that 140mg/L, fluid temperature are 38 ℃, current density 15A/dm ², electrolysis time 2 seconds.Figure 10 represents to have carried out the copper foil surface of this roughening treatment.

In a) operation, on the uneven surface of this electrolytic copper foil,, formed the rose vitriol electrolytic coating as a) operation.The forming process of rose vitriol electrolytic coating is as follows: the pH value of the rose vitriol (7 hydrate) of 20g/L is adjusted into 5.5, and using fluid temperature is that 27 ℃ rose vitriol electroplate liquid is bathed as stirring, and uses 1A/dm ²Current density carry out electrolysis in 12 seconds, (conversion thickness is 270mg/m thereby form gray rose vitriol electrolytic coating ²).Needn't adjust especially the concentration of cobalt ions in this moment solution.This is because what carry out is the short period of time electrolysis, so do not need to adjust concentration of metal ions.Figure 11 and Figure 12 represent the rose vitriol electrolytic coating that forms.Figure 11 has carried out the scanning electron microscope image that low range is observed, and Figure 12 has carried out the scanning electron microscope image that high magnification is observed.According to Figure 12 as can be known, apparently, the uneven surface shape of the electrolytic copper foil of substrate can be held clearly, and is appreciated that grey processing layer itself as thin as a wafer.

At b) in the operation, carry out shower type fully with pure water and clean, in reaching 150 ℃ drying oven, the temperature that makes environment by electricradiator stopped for 4 seconds, and remove moisture, thereby obtain to possess the surface treatment copper foil 1a of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained cross section shown in Figure 3, the cross-sectional height of this grey treated side (d) is 80nm, the L value of the Lab color specification system of this grey treated side is 41, and glossiness [Gs (60 °)] is 2.5.In addition, do not find uneven color at the grey treated side, the adhesive tape test by stickup, peel adhesion adhesive tape on this surface does not confirm dry linting yet.

Further, the grey treated side of the surface treatment copper foil that obtains is processed as the electromagnetic wave shielding silk screen that plasma display is used, can finds out blackization having implemented to judge when transparence is handled.Adopt the following method of substitution to observe, promptly, the black concentration that forms transparent resin tunicle grey treated side before is 0.9, on this grey treated side, apply redix as the transparent resin tunicle, and drying solidifies it, see through the epoxy resin layer that has solidified observe the grey treated side variation tone.Its result, the black concentration of observing the grey treated side is 1.5.

The manufacturing of the electromagnetic wave shielding silk screen that＜plasma display is used 〉

On two faces of the surface treatment copper foil that obtains as described above, paste dry type film as etchant resist.And, the overlapping mask (mask film) that is used to manufacture experimently the test usefulness of electromagnetic wave shielding conductive mesh on the dry type film of grey treated side side only, the silk screen spacing is 20 μ m, the web lines width is 10 μ m, the silk screen angle excursion is 45 °, and the conductive mesh pattern that possesses the silk screen electrode part is around carried out ultraviolet exposure.At this moment, carry out ultraviolet exposure by whole face simultaneously, become the material that development thereafter can't be removed the etch protection layer of opposing face., use alkaline solution carry out video picture, form etched pattern thereafter.

Then, use iron(ic) chloride etching solution, carry out the copper etching, thereafter, produce electromagnetic wave shielding conductive mesh by the release etch protective layer from grey treated side side as copper etchant solution.Consequently carried out not having the extraordinary etching of etch residue.The etching state of having represented to be used to estimate the test pattern (circuit of 13 μ m width) of etching at Figure 13.According to Figure 13 as can be known, obtain not have etch residue, the outstanding fabulous circuit of etching factor.

Embodiment 2

Present embodiment is made the second surface processing Copper Foil 1c that possesses as the zinc-nickel alloy layer of antirust processing layer as shown in Figure 6, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till forming the grey processing layer that forms by the rose vitriol electrolytic coating, because follow embodiment 1 identical, so antirust treatment condition only are described at this.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 1, is 270mg/m ²

At this, on the two sides of the Copper Foil after forming gray rose vitriol electrolytic coating on the single face of embodiment 1, use the zinc-nickel alloy plating bath to carry out electroplating processes, on the two sides, form the zinc-nickel alloy layer.Making the zinc-nickel alloy layer is that the single nickel salt of 2.0g/L, zinc pyrophosphate, potassium pyrophosphate concentration that zinc concentration is 0.5g/L are that 250g/L, fluid temperature are that 35 ℃, pH value are 10, current density is 5A/m adopting nickel concentration ²Condition under 5 seconds of electrolysis, evenly and smoothly electrolysis is on the two sides.

Then, identical with embodiment 1, carry out shower type fully with pure water and clean, in reaching 150 ℃ drying oven, the temperature that makes environment by electricradiator stopped for 4 seconds, remove moisture, thereby obtain to possess the surface treatment copper foil 1c of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 75nm, the L value of the Lab color specification system of this grey treated side is 39, and glossiness [Gs (60 °)] is 2.5.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Further, the grey treated side of the surface treatment copper foil that obtains is processed as the electromagnetic wave shielding silk screen that plasma display is used, can finds out blackization having implemented to judge when transparence is handled.The black concentration that forms the grey treated side before the transparent resin tunicle is 0.9, and the result who adopts the method for substitution evaluation identical with embodiment 1 is that the grey treated side can observe that to deceive concentration be 1.6 black.

Identical with embodiment 1, use the surface treatment copper foil that obtains to manufacture experimently electromagnetic wave shielding conductive mesh.Even consequently exist antirust processing layer also can not hinder etching operation, carried out not having the extraordinary etching of etch residue.

Embodiment 3

Present embodiment as shown in Figure 8, is made to possess as the zinc-nickel alloy layer of antirust processing layer and the second surface of chromate treating layer and is handled Copper Foil 1e, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till forming the grey processing layer that forms by the rose vitriol electrolytic coating, owing to identical, so antirust treatment condition only are described at this with embodiment 1.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 1, is 270mg/m ²

The formation of antirust processing layer, identical with embodiment 2, use the zinc-nickel alloy plating bath, on the two sides, formed after the zinc-nickel alloy layer, carry out chromate treating on the two sides.At this, adopt electrolytic chromate to handle, electrolytic condition is: chromic acid is that 5.0g/L, pH value are 11.5, fluid temperature is that 35 ℃, current density are 8A/dm ², electrolysis time is 5 seconds.

Then, after the formation of chromate coating finishes, carry out shower type fully with pure water and clean, in reaching 150 ℃ drying oven, the temperature that makes environment by electricradiator stopped for 4 seconds, remove moisture, thereby obtain to possess the surface treatment copper foil 1e of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 75nm, the L value of the Lab color specification system of this grey treated side is 40, and glossiness [Gs (60 °)] is 2.3.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm powder yet.

Further, the grey treated side of the surface treatment copper foil that obtains is processed as the electromagnetic wave shielding silk screen that plasma display is used, can finds out blackization having implemented to judge when transparence is handled.The black concentration that forms the grey treated side before the transparent resin tunicle is 0.9, and the result who adopts the method for substitution evaluation identical with embodiment 1 is that the grey treated side can observe that to deceive concentration be 1.5 black.

Embodiment 4

Present embodiment is made the second surface processing Copper Foil 1c that possesses as the zinc-cobalt alloy layer of antirust processing layer as shown in Figure 6, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till forming the grey processing layer that forms by the rose vitriol electrolytic coating, owing to identical, so antirust treatment condition only are described at this with embodiment 1.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 1, is 270mg/m ²

At this, on the two sides of the Copper Foil after forming gray rose vitriol electrolytic coating on the glossy surface of embodiment 1, use the zinc-cobalt alloy plating bath to carry out electroplating processes, on the two sides, form the zinc-cobalt alloy layer.Making the zinc-cobalt alloy layer is that the rose vitriol of 2.0g/L, zinc pyrophosphate, potassium pyrophosphate concentration that zinc concentration is 0.5g/L are that 250g/L, fluid temperature are that 35 ℃, current density are 5A/m adopting cobalt concentration ²Condition under 5 seconds of electrolysis, thereby evenly and smoothly electrolysis is on the two sides.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 80nm, the L value of the Lab color specification system of this grey treated side is 40, and glossiness [Gs (60 °)] is 2.5.In addition, do not find uneven color, do not confirm dry linting yet by the adhesive tape test of on this surface, pasting, divest adhesive tape at the grey treated side.

Further, the grey treated side of the surface treatment copper foil that obtains is processed as the electromagnetic wave shielding silk screen that plasma display is used, can finds out blackization having implemented to judge when transparence is handled.The black concentration that forms the grey treated side before the transparent resin tunicle is 0.93, and the result who adopts the method for substitution evaluation identical with embodiment 1 is that the grey treated side can observe that to deceive concentration be 1.6 black.

Embodiment 5

Present embodiment is made to possess as the zinc-cobalt alloy layer of antirust processing layer and the second surface of chromate treating layer and is handled Copper Foil 1e as shown in Figure 8, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till forming the grey processing layer that forms by the rose vitriol electrolytic coating, owing to identical, so antirust treatment condition only are described at this with embodiment 1.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 1, is 270mg/m ²

The formation of antirust processing layer, identical with embodiment 4, use the zinc-cobalt alloy plating bath, on the two sides, formed after the zinc-cobalt alloy layer, carry out chromate treating on the two sides.At this, adopt electrolytic chromate to handle, electrolytic condition is: chromic acid concentration is that 5.0g/L, pH value are 11.5, fluid temperature is that 35 ℃, current density are 8A/dm ², electrolysis time is 5 seconds.

Then, be through with after the formation of chromic salt, carry out shower type fully with pure water and clean, in the temperature that makes environment by electricradiator reaches 150 ℃ drying oven, stopped for 4 seconds, remove moisture, thereby obtain to possess the surface treatment copper foil 1e of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 82nm, the L value of the Lab color specification system of this grey treated side is 41, and glossiness [Gs (60 °)] is 2.4.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Embodiment 6

Present embodiment is different with embodiment 1, uneven surface to electrolytic copper foil is not implemented roughening treatment, below identical with embodiment 1, uneven surface side at electrolytic copper foil forms the grey processing layer that is formed by the rose vitriol electrolytic coating, make second surface shown in Figure 2 and handle Copper Foil 1b, carry out the evaluation identical with embodiment 1.Therefore, for the explanation of the operation identical, in this omission with embodiment 1.In addition, the conversion thickness of gray rose vitriol electrolytic coating is 268mg/m ²With Figure 11 and shown in Figure 12 identical, the form of observing the rose vitriol electrolytic coating that forms.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 78nm, the L value of the Lab color specification system of this grey treated side is 42, and glossiness [Gs (60 °)] is 2.5.In addition, do not find uneven color, do not confirm dry linting yet by the adhesive tape test of on this surface, pasting, divest adhesive tape at the grey treated side.

Identical with embodiment 1, use the surface treatment copper foil that obtains to manufacture experimently electromagnetic wave shielding conductive mesh.Consequently carried out the extraordinary etching that there is not obstacle in etching operation, does not have etch residue.

Embodiment 7

In the present embodiment, identical with embodiment 6, the glossy surface of electrolytic copper foil is not implemented roughening treatment, and uneven surface has been carried out the grey processing, make first surface shown in Figure 2 and handle Copper Foil 1b, confirm etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.

In the present embodiment, using the nominal thickness that obtains by the electrolysis copper-bath is the Copper Foil of 15 μ m.And using sulfuric acid concentration is 30 ℃ dilution heat of sulfuric acid as 150g/L, fluid temperature, Copper Foil is immersed in this solution 30 seconds carries out cleaning of surface.

Then, on the uneven surface of above-mentioned Copper Foil,, formed the rose vitriol electrolytic coating as a) operation.The forming process of rose vitriol electrolytic coating is as follows: use rose vitriol (7 hydrate) concentration as 20g/L, pH value be adjusted into 5.5, fluid temperature is that 27 ℃ rose vitriol electroplate liquid is bathed as stirring, and uses 2A/dm ²Current density carry out electrolysis in 6 seconds, (conversion thickness is 275mg/m thereby form gray rose vitriol electrolytic coating ²).Needn't adjust especially this moment to the concentration of cobalt ions in the solution.So this is because what carry out is that the short period of time electrolysis does not need to adjust concentration of metal ions.With Figure 11 and shown in Figure 12 identical, the form of observing the rose vitriol electrolytic coating that forms.

At b) in the operation, carry out shower type fully with pure water and clean, in reaching 150 ℃ drying oven, the temperature that makes environment by electricradiator stopped for 4 seconds, and remove moisture, thereby obtain to possess the surface treatment copper foil 1b of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 80nm, the L value of the Lab color specification system of this grey treated side is 39, and glossiness [Gs (60 °)] is 2.2.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Embodiment 8

In the present embodiment, identical with embodiment 6, the glossy surface to electrolytic copper foil does not carry out roughening treatment, and uneven surface has been carried out the grey processing, make first surface shown in Figure 2 and handle Copper Foil 1b, confirm etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.

Then, on the uneven surface of above-mentioned Copper Foil,, formed the rose vitriol electrolytic coating as a) operation.The forming process of rose vitriol electrolytic coating is as follows: use rose vitriol (7 hydrate) concentration to be 40g/L, the pH value is 5.5, and fluid temperature is that 27 ℃ rose vitriol electroplate liquid is bathed as stirring, and uses 1A/dm ²Current density carry out electrolysis in 12 seconds, (conversion thickness is 268mg/m thereby form gray rose vitriol electrolytic coating ²).At this moment, needn't adjust especially the carrying out of the concentration of cobalt ions in the solution.So this is because what carry out is that the short period of time electrolysis does not need to adjust concentration of metal ions.With Figure 11 and shown in Figure 12 identical, observe the form of the rose vitriol electrolytic coating that forms.

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 78nm, the L value of the Lab color specification system of this grey treated side is 40, and glossiness [Gs (60 °)] is 2.6.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Embodiment 9

Present embodiment as shown in Figure 7, is made the second surface processing Copper Foil 1d that possesses as the zinc-cobalt alloy layer of antirust processing layer, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till having formed the grey processing layer that forms by the rose vitriol electrolytic coating, since identical with embodiment 7, so antirust treatment condition only are described at this.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 7, is 268mg/m ²

At this, on the two sides of the Copper Foil after forming gray rose vitriol electrolytic coating on the single face of embodiment 7, on the two sides, form the zinc-cobalt alloy layer with the condition identical with embodiment 4.And, with embodiment 1 in the same manner, carry out shower type fully with pure water and clean, in the temperature that makes environment by electricradiator reaches 150 ℃ drying oven, stopped for 4 seconds, remove moisture, thereby obtain to possess the surface treatment copper foil 1d of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 80nm, the L value of the Lab color specification system of this grey treated side is 41, and glossiness [Gs (60 °)] is 2.4.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Embodiment 10

Present embodiment as shown in Figure 9, is made to possess as the zinc-cobalt alloy layer of antirust processing layer and the second surface of chromate treating layer and is handled Copper Foil 1f, confirms etching performance with etching method trial-production electromagnetic wave shielding conductive mesh shape.Therefore, till forming the grey processing layer that forms by the rose vitriol electrolytic coating, owing to identical, so antirust treatment condition only are described at this with embodiment 7.In addition, the conversion thickness of gray rose vitriol electrolytic coating is identical with embodiment 7, is 270mg/m ²

The formation of antirust processing layer is used the zinc-cobalt alloy electroplate liquid in the same manner with embodiment 4, after the two sides has formed the zinc-cobalt alloy layer, carries out the chromate treating identical with embodiment 5 on the two sides.

Then, after the formation of chromate coating finishes, carry out shower type fully with pure water and clean, in the temperature that makes environment by electricradiator reaches 150 ℃ drying oven, stopped for 4 seconds, remove moisture, thereby obtain to possess the surface treatment copper foil 1f of the extraordinary grey treated side of tone.In addition, between each above-mentioned operation, in principle, be provided with, prevent to bring into the solution of pretreatment procedure with the washing step that utilized pure water in 15 seconds

The physical property of＜surface treatment copper foil 〉

The result who observes the cross section of the surface treatment copper foil that possesses the grey treated side that obtains through above operation with the FIB device has obtained the cross section identical with cross section shown in Figure 3, the cross-sectional height of this grey treated side is 78nm, the L value of the Lab color specification system of this grey treated side is 40, and glossiness [Gs (60 °)] is 2.4.In addition, do not find uneven color at the grey treated side, by on this surface, paste, the adhesive tape test of peel adhesion adhesive tape do not confirm dry linting yet.

Industrial utilizability

The surface treatment copper foil that possesses the grey treated side that the present invention relates to, the uneven color that does not have the grey treated side, and can be from this surface picking, and can use common copper etchant solution to carry out etching and processing, the electromagnetic wave shielding conductive mesh of the front panel by being used in plasma display can form the high-quality black film that does not have uneven color. In addition, if can supply with the surface treatment copper foil that possesses the grey treated side, then can be omitted in the black treatment process in the manufacturing process of front panel. And this possesses the surface treatment copper foil of grey treated side, because adopt above-mentioned manufacture method, does not need new manufacturing equipment so can use the process of surface treatment of existing Copper Foil. Therefore, because can under the state that keeps high finished product rate, make the high-quality product that does not have uneven color, so can reduce production costs.

The simple declaration of accompanying drawing

Fig. 1 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Fig. 2 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Fig. 3 is that the FIB of cross-sectional layers structure that possesses the surface treatment copper foil of grey treated side observes image.

Fig. 4 is that the FIB of cross-sectional layers structure that possesses the surface treatment copper foil of grey treated side observes image.

Fig. 5 is the observation image of cross-sectional layers structure FIB that possesses the surface treatment copper foil of grey treated side.

Fig. 6 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Fig. 7 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Fig. 8 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Fig. 9 is the figure of cross-sectional layers structure that has schematically represented to possess the surface treatment copper foil of grey treated side.

Figure 10 is the scanning electron microscope image that has carried out the copper foil surface of roughening treatment.

Figure 11 carries out the electron microscope image that low range is observed to gray rose vitriol electrolytic coating.

Figure 12 carries out the electron microscope image that high magnification is observed to gray rose vitriol electrolytic coating.

Figure 13 is the scanning electron microscope image of etching test pattern.

Figure 14 is the synoptic diagram of manufacturing process of the front panel of the existing plasma display device of expression.

Figure 15 is the synoptic diagram of manufacturing process of the front panel of the existing plasma display device of expression.

Figure 16 is the synoptic diagram of manufacturing process of the front panel of the existing plasma display device of expression.

The explanation of Reference numeral

1a, 1b, 1c, 1d, 1e, 1f surface treatment copper foil

2 roughening treatment layers

3 fine shot coppers

4 rose vitriol electrolytic coatings

5 antirust processing layers (zinc-nickel alloy layer or zinc-cobalt alloy layer)

6 chromate treating layers

7 copper foil layers

Claims

1. a surface treatment copper foil possesses on the uneven surface of electrolytic copper foil the grey treated side is arranged, and it is characterized in that, this grey treated side is 200mg/m for the gravimetric thickness in the single face setting of copper foil layer ²～350mg/m ²The rose vitriol electrolytic coating, and the cross-sectional height of this grey treated side is below the 200nm, wherein, the layer that this rose vitriol electrolytic coating is to use cobalt sulfate solution to form by electrochemical plating.

2. surface treatment copper foil according to claim 1 is characterized in that, possesses antirust processing layer on above-mentioned grey treated side.

3. surface treatment copper foil according to claim 2 is characterized in that, antirust processing layer uses zinc or zinc alloy.

4. surface treatment copper foil according to claim 2 is characterized in that, antirust processing layer is that the layer and the chromate treating layer that form by using zinc or zinc alloy constitute.

5. surface treatment copper foil according to claim 1 is characterized in that, the L value of the Lab color specification system of above-mentioned grey treated side is below 43.

6. surface treatment copper foil according to claim 1 is characterized in that, above-mentioned grey treated side is to have formed this grey treated side on the uneven surface of electrolytic copper foil, and glossiness Gs60 ° is below 10.

7. surface treatment copper foil according to claim 1, it is characterized in that, the black concentration of above-mentioned grey treated side is 0.7～1.2, and this black concentration is based on the value that JIS B 9620, JIS B 9622 measure under the condition determination of state T, sampling point 1.5 * 2mm, no polarizing filter.

8. surface treatment copper foil according to claim 1 is characterized in that, above-mentioned grey treated side the transparent resin tunicle being adjacent to when disposing in its surface, can be recognized as black.

9. surface treatment copper foil according to claim 1, it is characterized in that, black concentration when being provided with the transparent resin tunicle on the grey treated side is more than 1.2, and this black concentration is based on the value that JIS B9620, JIS B 9622 measure under the condition determination of state T, sampling point 1.5 * 2mm, no polarizing filter.

10. the manufacture method of a surface treatment copper foil is the manufacture method that possesses the surface treatment copper foil of grey treated side, it is characterized in that, possess following a) and b) operation,

A) at the uneven surface of Copper Foil, use rose vitriol 7 hydrates that comprise 10g/L～40g/L, pH value is more than 4.0, fluid temperature is the stirring bath of the rose vitriol electroplate liquid below 30 ℃, with 4A/dm ²Following current density is carried out electrolysis, forms gray rose vitriol electrolytic coating,

Wash b) thereafter,, drying.

11. the manufacture method of a surface treatment copper foil is the manufacture method that possesses the surface treatment copper foil of the grey treated side that has antirust processing layer, it is characterized in that, possesses following a) to c) operation,

A) at the uneven surface of Copper Foil, use rose vitriol 7 hydrates that comprise 10g/L～40g/L, pH value is 4.0 or more, fluid temperature is that rose vitriol electroplate liquid below 30 ℃ is as the stirring bath, with 4A/dm ²Following current density is carried out electrolysis, forms gray rose vitriol electrolytic coating,

B) on the two sides of the Copper Foil that has formed gray rose vitriol electrolytic coating or single face, form antirust processing layer,

Wash c) thereafter,, drying.

12. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 1 and form is used.

13. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 2 and form is used.

14. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 3 and form is used.

15. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 4 and form is used.

16. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 5 and form is used.

17. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 6 and form is used.

18. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 7 and form is used.

19. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 8 and form is used.

20. the electromagnetic wave shielding conductive mesh that the front panel of a plasma display that uses the described surface treatment copper foil of claim 9 and form is used.