CN103963376A - Composite Copper Foil And Manufacturing Method Therefor - Google Patents

Composite Copper Foil And Manufacturing Method Therefor Download PDF

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Publication number
CN103963376A
CN103963376A CN201410025355.6A CN201410025355A CN103963376A CN 103963376 A CN103963376 A CN 103963376A CN 201410025355 A CN201410025355 A CN 201410025355A CN 103963376 A CN103963376 A CN 103963376A
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China
Prior art keywords
alligatoring
copper
copper foil
copper coating
coating
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CN201410025355.6A
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Chinese (zh)
Inventor
后藤千鹤
青山拓矢
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SH Copper Products Co Ltd
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SH Copper Products Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a composite copper foil and a manufacturing method therefor. At the same time of sustaining transmittance of substrate, high adaption witht the substrate is obtained. The composite copper foil is provided with a yoked copper foil, a copper coating layer formed on at least one face of the yoked copper foil and a coarsh copper coating layer formed on the copper coating layer and containing coarse grannula whose average diameter is greater than 0.05 micrometer and smaller than 0.30 micrometer. The ratio of the greater diameter to the smaller diameter of the coarse grannules is smaller than 65 percents. The coarse grannules distribute continuously in a distance larger than 20 micrometers and are connected on the copper coating layer in a cross section in the thickness direction of the coarse copper coating layer.

Description

The manufacture method of composite copper foil and composite copper foil
Technical field
The present invention relates to have copper coating and the composite copper foil of alligatoring copper coating and the manufacture method of composite copper foil.
Background technology
Flexible printing patch panel (FPC:Flexible Printed Circuit) is thin and pliability is excellent.Therefore, FPC great majority are for the first-class movable parts of kink, digital camera, printer of clamshell handset, in addition also for the distribution of the movable part of disk relevant device etc.
As the wiring material of FPC, use and to compare rolled copper foil that the resistance to bend(ing) of tolerance alternating bending is more excellent etc. with electrolytic copper foil etc.In the manufacturing process of FPC, the rolled copper foil that FPC uses waits and FPC basement membrane (base material) laminating consisting of resins such as polyimides by heating.
At this moment, in order to improve the adaptation of rolled copper foil and FPC base material, the alligatoring copper coating that comprises alligatoring grain is for example set at least one side of rolled copper foil sometimes.Increase the particle diameter of alligatoring grain and increase the surface roughness of rolled copper foil, due to anchor effect, more improve with the adaptation of base material.While forming alligatoring copper coating, sometimes copper coating is set on rolled copper foil and smoothing in advance (for example patent documentation 1,2) in advance.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-238647 communique
Patent documentation 2: TOHKEMY 2006-155899 communique
Summary of the invention
The problem that invention will solve
Yet, if it is excessive to have the surface roughness of composite copper foil of copper coating, alligatoring copper coating, have the concavo-convex situation that is transferred to the base material that is fitted with composite copper foil at composite copper foil.The light transmittance of the irregular base material of transfer printing reduces, and when FPC being installed on electronic equipment etc., may hinder contraposition.
On the other hand, if reduce the alligatoring grain etc. of alligatoring copper coating and the surface roughness of composite copper foil is diminished, can not fully obtain the adaptation with base material, the reliability of the distribution consisting of composite copper foil reduces.
The object of the present invention is to provide a kind of composite copper foil of high adhesion and manufacture method of composite copper foil that can obtain with base material when maintaining the light transmittance of base material.
The method of dealing with problems
According to the 1st mode of the present invention, a kind of composite copper foil is provided, have:
Rolled copper foil,
The copper coating forming at least one side of the rolling Copper Foil, and
What on above-mentioned copper coating, form comprises the alligatoring copper coating that average grain diameter is more than 0.05 μ m alligatoring grain below 0.30 μ m;
The poor ratio of the maximum particle diameter of above-mentioned alligatoring grain and the particle diameter of minimum grain size is below 65%,
The cross section that above-mentioned alligatoring copper coating is blocked from thickness direction, form following state: the above-mentioned alligatoring grain continuously distance more than 20 μ m does not interrupt and is connected on above-mentioned copper coating,
Wherein, poor ratio (%)=(1-minimum grain size/maximum particle diameter) * 100 of particle diameter.
According to the 2nd mode of the present invention, a kind of composite copper foil is provided, have:
Rolled copper foil,
The copper coating forming at least one side of the rolling Copper Foil, and
What on above-mentioned copper coating, form comprises the alligatoring copper coating that average grain diameter is more than 0.05 μ m alligatoring grain below 0.30 μ m;
The poor ratio of the maximum particle diameter of above-mentioned alligatoring grain and the particle diameter of minimum grain size is below 65%,
Utilize scanning electron microscope, the area without forming section of the above-mentioned alligatoring grain existing in the visual field of 10,000 times of multiplying powers is 5 μ m 2below,
Wherein, poor ratio (%)=(1-minimum grain size/maximum particle diameter) * 100 of particle diameter.
According to the 3rd mode of the present invention, the composite copper foil described in the a kind of the 1st or the 2nd mode is provided,
In the situation that the surface of above-mentioned copper coating exists recess, the mean value of the degree of depth of above-mentioned recess is below 0.60 μ m.
According to the 4th mode of the present invention, the composite copper foil described in any one in a kind of the 1st～3rd mode is provided, above-mentioned copper coating use has been added the copper electrolyte of organosulfur compound, surfactant, levelling agent and the chloride ion with sulfydryl and has formed.
According to the 5th mode of the present invention, the composite copper foil described in any one in the 1st～4th mode is provided, when above-mentioned alligatoring copper coating is flattened equably, be equivalent to the thickness below the above 0.25 μ m of 0.05 μ m.
According to the 6th mode of the present invention, the composite copper foil described in any one in the 1st～5th mode is provided, on above-mentioned alligatoring copper coating, having thickness is the antirust coat below the above 70nm of 11nm.
According to the 7th mode of the present invention, composite copper foil described in any one in the 1st～6th mode is provided, on above-mentioned alligatoring copper coating, be formed with successively nickel coating, zinc coating, chromium processing layer and silane coupled processing layer, and to have thickness be the antirust coat below the above 70nm of 11nm.
According to the 8th mode of the present invention, a kind of manufacture method of composite copper foil is provided, have:
On at least one side of rolled copper foil, form the operation of copper coating, and
On above-mentioned copper coating, form and comprise the operation that average grain diameter is more than 0.05 μ m alligatoring copper coating of the alligatoring grain below 0.30 μ m;
In forming the operation of above-mentioned copper coating,
With the copper electrolyte that has added organosulfur compound, surfactant, levelling agent and the chloride ion with sulfydryl, form above-mentioned copper coating.
The effect of invention
According to the present invention, provide a kind of composite copper foil of high adhesion and manufacture method of composite copper foil that can obtain with base material when maintaining the light transmittance of base material.
Accompanying drawing explanation
Fig. 1 means the flow chart of the manufacturing process of the composite copper foil that an embodiment of the invention relate to.
Fig. 2 upper semisection is the surface observation photo of the alligatoring paper tinsel that relates to of embodiments of the invention 8, and lower semisection is the surface observation photo of the alligatoring paper tinsel that relates to of comparative example 4.
Fig. 3 upper semisection is that the section of the alligatoring paper tinsel that relates to of embodiments of the invention 8 is observed photo, and lower semisection is that the section of the alligatoring paper tinsel that relates to of comparative example 4 is observed photo.
Fig. 4 is the schematic diagram that is illustrated in coarsening-free omission state on alligatoring copper coating.
Fig. 5 means the surface observation photo of fine or not FPC of the observability of light transmission rate in FPC base material and distribution.
Fig. 6 means that the section of the FPC in the gap that the laminating of the composite copper foil that relates to by prior art and FPC base material produces observes photo.
The specific embodiment
The opinion that the inventor etc. obtain
As mentioned above, in order to improve the adaptation with FPC base material, sometimes use the composite copper foil that is formed with successively copper coating and alligatoring copper coating at least one side of rolled copper foil.In order to form such alligatoring copper coating, for example on rolled copper foil, form copper coating and carry out after smoothing, carry out for example roughening treatment of plating under the current density more than critical current density in copper electrolyte.Thus, at the surface attachment alligatoring grain of copper coating and form concaveconvex shape.For example the current value when improving roughening treatment or be divided into several stages and implement roughening treatment, can increase particle diameter, can control surface roughness.
At this moment, if alligatoring largeization of granulated fertilizer that alligatoring copper coating has and the surface roughness of composite copper foil is too become greatly, the concavo-convex base material that is fitted with composite copper foil that is transferred on surface sometimes, the light transmittance of base material reduces.On electronic equipment etc. during actual installation FPC, such as by CCD camera etc., see through that FPC base material confirms the composite copper foil that fits in base material to remove a part and the contraposition with electronic equipment is carried out in the distribution position that forms.If remove composite copper foil, thereby being transferred to the light transmittance of the base material base material exposing, reduce composite copper foil concavo-convex, contraposition expends time in and makes actual installation practice Efficiency Decreasing, or becomes and can not carry out contraposition at all.The situation of using metallurgical microscopes to observe it is shown in to Fig. 5.
As shown in Fig. 5 (a), if the light transmittance of base material keeps good state, according to the deep or light difference in viewing area can confirm clearly distribution end, be the border of distribution and base material.On the other hand, shown in Fig. 5 (b), owing to making concavo-convex being transferred, the situation that the light transmittance of base material reduces with the laminating of the large composite copper foil of surface roughness.Find, represent that distribution and the deep or light of base material border become indefinite.Be explained, about the extremely little situation of alligatoring grain shown in Fig. 5 (c) as described later.
In the composite copper foil that the inventor etc. use at FPC, in order to eliminate such undesirable condition, attempt shortening as far as possible the plating time of roughening treatment and suppress the growth of the alligatoring grain that alligatoring copper coating has.
Yet if want to reduce the alligatoring grain that alligatoring copper coating has, what on copper coating, local not part, the alligatoring grain of plating of generation do not grown sometimes is the part that alligatoring is omitted without growth part.With regard to alligatoring grain without with regard to growth part, surface roughness extremely reduces.In addition, like this without growth part, between composite copper foil and base material, easily produce gap.Thus, between composite copper foil and base material, can not obtain sufficient anchor effect, adaptation reduces.Sometimes there is the situation that when FPC is immersed in medicine etc., medicine durability reduces.Fig. 6 is illustrated in the situation that produces gap between composite copper foil and base material.
In addition, if exist like this without growth part, the relief pattern of composite copper foil that is sometimes transferred to base material is uneven, when FPC contraposition, produces uneven on deep or light and the observability of distribution is reduced when seeing through base material and observe.Above-mentioned Fig. 5 (c) is due to the extremely little example that observability is reduced of alligatoring grain.In the example shown in Fig. 5 (c), see that wiring part divides shinny, the border of distribution becomes and is difficult to identification.
The inventor etc. are further investigation repeatedly further, finds out that it is be subject to as the state impact of the copper coating of bottom and produce that above-mentioned alligatoring is omitted.That is, expect by the state of copper coating is rationalized, can suppress such alligatoring and omit.In addition, the inventor waits the method for also having found to form copper coating under the state that can suppress alligatoring omission.
The present invention waits the invention of these opinions of finding based on inventor.
An embodiment of the invention
(1) formation of composite copper foil
The formation of the composite copper foil first, an embodiment of the invention being related to describes.
The alligatoring copper coating that the composite copper foil of present embodiment has rolled copper foil, the copper coating forming at least one side of rolled copper foil and forms on copper coating.In addition, the composite copper foil that present embodiment relates to has antirust coat on alligatoring copper coating.
The composite copper foil like this forming, for example, be formed with alligatoring face side and the laminating of FPC base material of alligatoring copper coating, in the purposes for FPC as flexual wiring material.
(summary of rolled copper foil)
The rolled copper foil that composite copper foil has is for example configured to by having tabular as the rolling surface of first type surface.This rolled copper foil is, such as implementing hot-rolled process, cold rolling process etc. as the ingot casting of raw material and form the rolled copper foil of specific thickness usining the fine copper such as oxygen-free copper (OFC:Oxygen-Free Copper), tough pitch copper (FPC:tough pitch copper).For the related rolled copper foil of present embodiment, if embodiment when doubled as the recrystallization annealing operation with the bonding process of FPC base material, expects modifiedly have excellent resistance to bend(ing) for recrystallization.
As the raw-material oxygen-free copper of rolled copper foil, such as the purity for defineds such as JIS C1020, H3100, be more than 99.96% copper material.Oxygen content can be not exclusively zero, for example, can contain the oxygen of several ppm degree.In addition, the raw-material tough pitch copper as rolled copper foil is more than 99.9% copper material such as the purity for defineds such as JIS C1020, H3100.The in the situation that of tough pitch copper, oxygen content is for example 100ppm～600ppm left and right.Or, as rolled copper foil, can use the interpolation material of regulations such as adding micro-tin (Sn), silver (Ag), boron (B), titanium (Ti) in oxygen-free copper, tough pitch copper and make low concentration copper alloy and adjusted the raw material of the various characteristicses such as heat resistance.
(summary of copper coating)
For the copper coating having for composite copper foil, on the surface of at least one side at the rolling surface as rolled copper foil first type surface or its back side, such as using to electroplate etc., form.In addition, the copper coating that present embodiment relates to for example thickness is below the above 0.4 μ m of 0.1 μ m.
Thickness by making copper coating, for for example more than 0.1 μ m, becomes easy thereby implement equably alligatoring copper plating (roughening treatment) on copper coating.On the other hand, by copper coating being made as below 0.4 μ m, thereby electroplating time can be elongated necessarily, can boost productivity.In addition, after heat treatment, can more positively improve the resistance to bend(ing) of composite copper foil integral body.This is fully thin owing to being difficult to the copper coating of recrystallization, therefore, is difficult for hindering the raising of the resistance to bend(ing) of rolled copper foil.
In addition, especially, as described later, the copper coating use that present embodiment relates to has been added the copper electrolyte of organosulfur compound, surfactant and the chloride ion with sulfydryl and has formed.Thus, at least for example in the situation that the surface of copper coating exists recess, the mean value of the maximum gauge of recess is below 20 μ m, is preferably below 15 μ m, and the mean value of recess depths is below 0.6 μ m, is preferably below 0.5 μ m.Here, with regard to the shape of the plan view of the recess on copper coating surface, for example, obtaining not being just to justify but during oval shape, the diameter of recess is being defined as to maximum gauge.
As described later, the inventor etc. think, even make alligatoring grain at least 1 reason that extremely little alligatoring copper coating also can suppress in reason that alligatoring omits be that so making the surperficial recess depths of copper coating is below setting.
(summary of alligatoring copper coating)
The alligatoring copper coating that composite copper foil has forms on copper coating.By making composite copper foil there is alligatoring copper coating, can improve the adaptation of composite copper foil and FPC base material.
Alligatoring copper coating is mainly to consist of the alligatoring grain adhering to by plating on copper coating.Alligatoring grain such as for copper (Cu) simple substance or in copper (Cu), comprise in iron (Fe), molybdenum (Mo), nickel (Ni), cobalt (Co), cadmium (Cr), zinc (Zn), tungsten (W) etc. more than at least a kind, preferred metallic of more than two kinds.By comprising like this other metallic, therefore can suppress alligatoring grain is grown to dendroid (branch is crystalline).
The average grain diameter of alligatoring grain is for example below the above 0.3 μ m of 0.05 μ m.In addition, the poor ratio of the maximum particle diameter of alligatoring grain and the particle diameter of minimum grain size is below 65%.Wherein, poor ratio (%)=(1-minimum grain size/maximum particle diameter) * 100 of particle diameter.That is to say, mean that the poor ratio of particle diameter is less, the maximum particle diameter of alligatoring grain and the difference of minimum grain size are less.
With regard to the thickness of the alligatoring copper coating that contains irregular each alligatoring grain of tool, if each alligatoring grain is flattened equably, be for example equivalent to 0.05 μ m above and be less than 0.26 μ m, the preferably thickness below the above 0.25 μ m of 0.05 μ m.
More than the thickness of alligatoring copper coating is located to 0.05 μ m, can obtains sufficient anchor effect and improve the adaptation with base material.On the other hand, by alligatoring copper coating is made as, being less than 0.26 μ m, is further below 0.25 μ m, and the surface roughness that can suppress composite copper foil becomes excessive.In addition, electroplating time also can be elongated necessarily, can boost productivity.In addition, by making alligatoring copper coating not blocked up, also easily maintain the resistance to bend(ing) as composite copper foil integral body.
In addition, in alligatoring copper coating, in alligatoring grain, do not grow without growth part, be the repressed state of generation that alligatoring is omitted.This can learn by the situation of for example using SEM (SEM:ScanningElectron Microscopy) observation alligatoring copper coating to become following state.
That is, in alligatoring, omit in repressed alligatoring copper coating, the cross section that alligatoring copper coating is blocked from thickness direction, form following state: the alligatoring grain continuously distance more than 20 μ m does not interrupt and is connected on copper coating.At this moment, alligatoring grain is in 1 of copper coating upper semisection accumulation or a plurality of and grow.Therefore, so-called alligatoring grain does not interrupt, and for example comprises as shown in Figure 4 (a), and the alligatoring grain 20 being attached directly on copper coating 10 is mutual not discretely in abutting connection with connected state.In addition, so-called alligatoring grain does not interrupt, comprise for example as shown in Figure 4 (b), even if the alligatoring grain 20 being attached directly on copper coating 10 does not mutually connect and becomes scattered, but by further adhering to 1 above alligatoring grain 20 thereon, thereby alligatoring grain 20 continues connected state along copper coating 10 surfaces.In addition, above state as long as can confirm the cross section of blocking from any direction.Or, preferably in any or two in and cross section that vertically block parallel with rolling direction, form above-mentioned state.
Or, in alligatoring, omit in repressed alligatoring copper coating, utilize SEM, the area without forming section of the alligatoring grain existing in the visual field of 10,000 times of multiplying powers becomes below 5 μ m2, is preferably below 2 μ m2.Alligatoring grain without forming section, can not confirm the granular profile of alligatoring grain, the copper coating by bottom becomes the state exposing and distinguishes.The area without forming section of alligatoring grain is the summation in the visual field of 10,000 times of multiplying powers.
When meeting the either party of these 2 kinds of states or two sides, can say the adaptation that fully obtains alligatoring copper coating and base material, in alligatoring, omit repressed state.That is, become the state that surface roughness is fully maintained, gap other and base material is difficult to generation of composite copper foil.
(summary of antirust coat)
The antirust coat that composite copper foil has has the stepped construction that is for example formed with successively nickel coating, zinc coating, chromaking processing layer (3 valency chromium chemical synthesis processing layer), silane coupled processing layer on alligatoring copper coating.Antirust coat is for example equivalent to 0.1g/m in plating amount 2above 0.6g/m 2following thickness, that is to say as the thickness below the above 70nm of 11nm.More particularly, for example making nickel coating is the thickness below the above 50nm of 9nm, and zinc coating is the thickness below the above 10nm of 1nm, and chromaking processing layer is the thickness below the above 10nm of 1nm.Silane coupled processing layer is layer as thin as a wafer.
By making composite copper foil there is antirust coat, can improve heat resistance, the resistance to chemical reagents of composite copper foil.At this moment, by the thickness of antirust coat is located within the scope of afore mentioned rules, can access sufficient heat resistance, resistance to chemical reagents, can not hinder the easiness of etching method simultaneously.
In addition, specifically, in forming each layer of antirust coat, nickel coating suppresses the diffusion of copper.In addition, zinc coating improves heat resistance.In addition, chromaking processing layer and silane coupled processing layer work as chemical synthesis processing layer (chemical synthesis processing epithelium).Particularly silane coupled processing layer can improve the chemical adaptation of composite copper foil and base material.
In addition, even only in the situation that the one side of rolled copper foil forms copper coating, alligatoring copper coating, also can form such antirust coat in a side that is formed with alligatoring copper coating etc., at least a portion that simultaneously forms such antirust coat on the face of the side on the other hand of rolled copper foil is nickel coating, zinc coating, chromaking processing layer for example.Thus, even in the side without copper coating etc. of composite copper foil, also can improve heat resistance, resistance to chemical reagents.
(effect suppressing is omitted in alligatoring)
In composite copper foil as constructed as above, the alligatoring of alligatoring copper coating is omitted to the effect suppressing, illustrate as follows.
When alligatoring copper coating forms, if do one's utmost to shorten the plating time of roughening treatment, suppress the growth of alligatoring grain and form little alligatoring grain, as mentioned above, have and on alligatoring copper coating, produce the situation that alligatoring is omitted.Thus, the border observability of the adaptation of composite copper foil and base material, distribution reduces sometimes.
The inventor etc. further investigate, and found that: if by using the method for aftermentioned regulation to form copper coating, and using it as bottom, can form alligatoring and omit repressed alligatoring copper coating.That is to say, by the method for regulation, can under the state that can suppress alligatoring omission, form copper coating.Contributing to of bringing about the concrete state of copper coating at this moment and this state, is suppressed structure that alligatoring omits in further research.
Wherein, the discoveries such as the inventor: in this copper coating, the small depression at least existing on copper coating, be that the degree of depth of surface voids is compared and diminished with the copper coating forming by additive method.Further, the inventor waits and has confirmed that the major part that these alligatoring are omitted is the recess surface generation that surpasses prescribed level on copper coating.
The surface voids of such copper coating is thought to be originally present in the oil hole (Oil-pit) on rolled copper foil surface etc. and by copper coating, is not filled up and residual recess completely.The ROLLING OIL that oil hole is used during for rolling is for example engaged to by Rolling roller the depression that the surface of the sheet material of rolling object produces.The degree of depth in the oil hole on rolled copper foil surface is for example below the above 1.0 μ m of 0.7 μ m.
The inventor etc. produce alligatoring omission to the recess surface such and study as follows.
Under the current density of roughening treatment more than critical current density, carry out.Therefore think, as a little concavo-convex electric field that causes of the copper coating of bottom, be affected.That is to say, at protuberance electric current, easily concentrate, plating is easily grown.On the other hand, at valley current, be difficult to concentrate, plating is difficult to growth.
Thus, the inventor etc. think: if the recess existing on copper coating surface surpasses above-mentioned prescribed level, on the surface of recess, easily produce alligatoring and omit.At this moment think, alligatoring grain is got over miniaturization, is more easily subject to a little concavo-convex impact of copper coating.
On the other hand, the edge of recess etc. becomes convex form, at such protuberance, has following worry: largeization of alligatoring granulated fertilizer, or alligatoring grain to be grown to branch crystalline, the concavo-convex increase of alligatoring copper coating thus, it is excessive that surface roughness becomes.
In order to solve problem as above, the copper coating that present embodiment relates to is that mode below setting forms according to the size of recess on surface at least.Thus, even if do one's utmost to shorten the plating time of roughening treatment, make alligatoring grain extremely little, also can suppress alligatoring omission etc.The maximum particle diameter of alligatoring grain and the difference of minimum grain size also easily reduce.
In addition, because the size of the recess on copper coating surface becomes below setting, can reduce the poor of the maximum particle diameter of alligatoring grain and minimum grain size, that is to say, reduce the poor ratio of particle diameter of being obtained by above-mentioned formula, in addition, can suppress the generation of ingotism etc.
Wherein think, in the present embodiment, because alligatoring grain is fine, therefore, although easily there is alligatoring omission etc., be difficult for occurring the misgrowths such as ingotism.Therefore think, as mentioned above, if the degree of depth that makes recess for for example below 0.6 μ m, misgrowth is certain repressed state substantially, and can fully reduce alligatoring omission.If the degree of depth of recess, for for example below 0.5 μ m, can more positively suppress misgrowth.
In addition, as described later, the inventor etc. are also clear and definite, easy recrystallization in the recrystallization annealing operation that the copper coating forming by prescriptive procedure carries out in the manufacturing process of FPC.On the other hand, major part can not recrystallization in same operation for the copper coating forming by additive method.Therefore, can say for the copper coating relating to for present embodiment, as intrinsic state, have potentially the state of so easy recrystallization, another essential factor of inhibition is omitted in this alligatoring that is also considered to alligatoring copper coating.
(2) manufacture method of composite copper foil
The inventor etc. conduct in-depth research in order to form the copper coating of the alligatoring omission that can suppress alligatoring copper coating.Its result, has obtained the effect of regulation, so has here described by following method.
The manufacture method of the composite copper foil that an embodiment of the invention are related to, is used Fig. 1 to describe.Fig. 1 means the flow chart of the manufacturing process of the composite copper foil that present embodiment relates to.
(the preparatory process S10 of rolled copper foil)
As shown in Figure 1, first prepare the rolled copper foil as former paper tinsel.About rolled copper foil, as mentioned above, by the fine copper being formed by oxygen-free copper, tough pitch copper or using they as low concentration copper alloy of parent phase etc. as raw material.To the ingot casting enforcement hot-rolled process of this raw material, the operation of repeatedly carrying out cold-rolling treatment and annealing in process and final cold rolling process, obtain the rolled copper foil of specific thickness.
(the formation operation S20 of copper coating)
Then, carry out electrolytic degreasing and pickling processes S21 and copper plating treatment S22, carry out forming the copper coating formation operation S20 of copper coating at least one side of rolled copper foil.In addition, between reason, implementing throughout washing processes.
That is, carry out electrolytic degreasing and pickling processes S21 and the surface clean of rolled copper foil is clean.As electrolytic degreasing, such as aqueous slkalis such as using NaOH, carry out catholyte degreasing.As aqueous slkali, for example can use the aqueous solution of the sodium carbonate below the above 30g/L of NaOH, 10g/L containing below the above 60g/L of 20g/L.
As pickling processes, such as rolled copper foil being immersed in the acidic aqueous solutions such as sulfuric acid, to remaining in the alkali composition on rolled copper foil surface, neutralize and copper oxide-film is removed.As acidic aqueous solution, such as using acidic aqueous solution, copper etchant solutions etc. such as containing the following sulphur aqueous acid of the above 180g/L of 120g/L, citric acid.
Then, carry out copper plating treatment S22, on rolled copper foil, form copper coating.As copper plating treatment S22, for example, implement to using the electrolytic treatments of rolled copper foil as negative electrode in bathing take acid copper-plating that copper sulphate and sulfuric acid is main component.
At this moment, the solution composition of acid copper plating bath, solution temperature, electrolytic condition can be selected from broad range, are not particularly limited, for example, preferably from following ranges, select.
Below the above 300g/L of copper sulfate pentahydrate: 20g/L
Below the above 200g/L of sulfuric acid: 10g/L
Solution temperature: 15 ℃ above below 50 ℃
Current density: 2A/dm 2above 15A/dm 2below
Processing time: below above 20 seconds in 1 second
In addition, more preferably, can make copper sulfate pentahydrate is that the above 300g/L of 50g/L is following, to make sulfuric acid be that the above 200g/L of 30g/L is with inferior.
Be explained, current density is at this moment less than critical current density.That is to say, be made as the current density that ashing (ヤ ケ め っ I) can not occur what is called.Like this by being made as the current density that is less than critical current density, can make copper coating surface concavo-convex little, realize smoothing.But the higher plating speed of current density is higher, productivity ratio improves.Therefore, in the plating condition of regulation, be preferably made as and be less than critical current density and for high as far as possible current density.
At this moment, by being made as in the processing time below above 20 seconds in 1 second, the thickness that for example can make copper coating is below the above 0.4 μ m of 0.1 μ m.
In addition, in above-mentioned acid copper plating bath, add the organic system additive of regulation.As organic system additive, such as 3-sulfydryl-1-sulfonic acid (being called MPS below), two (3-sulfonic acid propyl group) disulphide (being called SPS below) etc. being had to the compound of sulfydryl, the chloride ions such as the levelling agents such as the surfactants such as polyethylene glycol, polypropylene glycol, diallyldialkylammonihalide alkyl sulfate, hydrochloric acid (the HCl aqueous solution) are used in combination with regulation.
Specifically, can use combination have powder reagent as pair (the 3-sulfonic acid propyl group) disulphide below the above 40mg/L of 5mg/L of organosulfur compound, as the polypropylene glycol below the above 4ml/L of 1ml/L of surfactant, as the diallyldialkylammonihalide alkyl sulfate below the above 2.0g/L of 0.1g/L of levelling agent, as the additive of the hydrochloric acid below the above 0.3ml/L of 0.05ml/L of chloride ion etc.
In addition at this moment, also can use the additive etc. for copper facing that is combined with in advance these organic system additives.As such copper facing additive, such as enumerating the TOPLUCINA LS of Okuno Chemical Industries Co., Ltd.'s system, the COPPER GLEAM CLX of MelTex Co., Ltd. system, the CU-BRITETH-RIII of Co., Ltd. of Ren Yuanyou Gilat system, the THRU-CUP EUC of C. Uyemura & Co Ltd's system etc.Can be by them any with normal concentration, regulation proportioning or use with above-mentioned various additive combinations.
As the example that uses such copper facing with additive, can use contain as two (the 3-sulfonic acid propyl group) disulphide below the above 60mg/L of 10mg/L of organosulfur compound, as for example molal weight below the above 300mg/L of 50mg/L of surfactant be polyethylene glycol about 3000g/mol, as the CU-BRITETH-RIII of Co., Ltd. of the Ren Yuanyou Gilat system below the above 10ml/L of 3ml/L of levelling agent, as the salt aqueous acid below the above 0.3ml/L of 0.05ml/L of chloride ion.
These organic system additives, in copper plating treatment, are the materials as brightener, surfactant.Yet, the discoveries such as the inventor, by by these organic system additives with being used in combination of regulation, the copper coating of formation becomes can suppress the state that alligatoring is omitted.In such state, comprise that the degree of depth of the recess on copper coating surface becomes below setting.That is to say and think, at least by the effect of above-mentioned organic system additive, the effect of the depressions such as oil hole by copper coating landfill rolled copper foil improves, and the recess size that can make to be present in copper coating surface is little.
The suppositions such as the inventor, may particularly have the effect of depression of the preferred landfill rolled copper foil of compound promoted of sulfydryl.This effect with sulfhydryl compound also has the synergistic possibility that causes further raising chloride ion.In the situation that not using these organic system additives, because the size of recess can not be suppressed in above-mentioned scope, its successful.
In addition, the discoveries such as the inventor, by by these organic system additives with being used in combination of regulation, in FPC manufacturing process, carry out in recrystallization annealing operation, rolled copper foil not only, copper coating also carries out recrystallization.The suppositions such as the inventor: when copper coating forms, by these organic system additives, needed some energy of recrystallization of copper coating is accumulated on copper coating.At this moment, by reducing surfactant, cause that the self-annealing (Self-annealing) of copper coating carry out the threshold value of the phenomenon of recrystallization at normal temperatures naturally, thereby exist copper coating to become the possibility of easy recrystallization state.Thus, at least can further improve the resistance to bend(ing) of composite copper foil.In addition, furtheing investigate by copper coating and thering is potentially the state of easy recrystallization and the alligatoring of alligatoring copper coating is omitted to the impact of inhibition.
These effects, purposes, using method that the inventor etc. find, compare with effect, purposes, using method before brightener as these organic system additives, surfactant etc., is diverse novel teachings.
By upper, form the rolled copper foil with copper coating that present embodiment relates to.
(the formation operation S30 of alligatoring copper coating)
Then, carry out forming the alligatoring copper coating formation operation S30 of alligatoring copper coating on copper coating.In addition, between reason, implementing throughout washing processes.
That is, for example implement to using rolled copper foil in the acid copper plating bath that copper sulphate and sulfuric acid is main component as the electrolytic treatments of negative electrode take, thereby alligatoring grain is attached to the surface of copper coating.
At this moment, the solution composition of acid copper plating bath, solution temperature, electrolytic condition can be selected from broad range, are not particularly limited, for example, preferably from following ranges, select.
Below the above 300g/L of copper sulfate pentahydrate: 20g/L
Below the above 200g/L of sulfuric acid: 10g/L
Solution temperature: 15 ℃ above below 50 ℃
Current density: 20A/dm 2above 100A/dm 2below
Processing time: 0.3 second is above and be less than for 2.0 seconds
In addition, current density is at this moment for surpassing the value of critical current density.That is to say, under the current value that so-called ashing occurs, carry out roughening treatment.
In addition, by being made as in the processing time below above 2.0 seconds in 0.3 second, for example, alligatoring grain is flattened equably, can be formed 0.05 μ m above and be less than the thickness of 0.26 μ m.Preferably will be made as in the processing time below above 1.3 seconds in 0.3 second, thereby alligatoring granulosa forms the thickness below the above 0.25 μ m of 0.05 μ m.
In addition, in above-mentioned acid copper plating bath, preferably add copper removal (Cu) metallic element in addition.As copper removal (Cu) metallic element in addition, such as enumerating iron (Fe), molybdenum (Mo), nickel (Ni), cobalt (Co), cadmium (Cr), zinc (Zn), tungsten (W) etc., in copper (Cu), can add these more than at least a kind, preferably two or more.
Specifically, can use the aqueous solution that comprises the ferric sulfate heptahydrate below the above 30g/L of 10g/L.
In the formation operation S30 of alligatoring copper coating, the copper coating with afore mentioned rules state is implemented to roughening treatment as bottom.Therefore,, during roughening treatment, what be difficult for generation alligatoring grain is that alligatoring is omitted without growth part.Thus, form the alligatoring copper coating that comprises the fine alligatoring grain with excellent homogeneity.At this moment, the maximum particle diameter of alligatoring grain and the difference of minimum grain size also reduce.
By upper, on copper coating, form alligatoring copper coating.
(the formation operation S40 of antirust coat)
Then, carry out Nickel Plating Treatment S41, zinc-plated treatment S 42, chromaking and process (3 valency chromium chemical syntheses are processed) S43 and silane coupled treatment S 44, thereby carry out forming the formation operation S40 of the antirust coat of antirust coat on alligatoring copper coating.This antirust coat is also referred to as post processing coating.In addition, between reason, implementing throughout washing processes.
In Nickel Plating Treatment S41, for example, can use the boron aqueous acid below the above 60g/L of nickel chloride, 40g/L below the above 50g/L of nickel sulfate hexahydrate compound, 40g/L containing below the above 320g/L of 280g/L.Thus, on alligatoring copper coating, form nickel coating.At this moment, also can add the compound that comprises other metallic elements such as cobalt, form the nickel coating being formed by nickel alloy.
In zinc-plated treatment S 42, for example, can use the aqueous solution of the sodium sulphate below the above 80g/L of zinc sulfate, 60g/L containing below the above 120g/L of 80g/L.Thus, on nickel coating, form zinc coating.At this moment, also can add the compound that comprises other metallic elements, form the zinc coating being formed by kirsite.
Afterwards, by chromaking treatment S 43, use the response type chromium plating liquid of 3 valency chromium types, on zinc coating, form chromaking processing layer (3 valency chromium chemical synthesis processing layer).In addition, as silane coupled treatment S 44, use silane coupling solution, on chromaking processing layer, form silane coupled processing layer.
Under above condition, adjust respectively the time, for example, nickel coating is formed to the thickness below the above 50nm of 10nm, zinc coating is formed to the thickness below the above 10nm of 1nm, chromaking processing layer is formed to the thickness below the above 10nm of 1nm.Then further form silane coupled processing layer as thin as a wafer.
By upper, the antirust coat that is formed with successively nickel coating, zinc coating, chromaking processing layer, silane coupled processing layer on alligatoring copper coating forms the thickness below the above 70nm of 12nm.
In addition, by upper, manufacture the alligatoring paper tinsel of the composite copper foil relating to as present embodiment.
(3) manufacture method of flexible printing patch panel
Then, to having used the manufacture method of flexible printing patch panel (FPC) of the composite copper foil of the embodiment the present invention relates to describe.
(recrystallization annealing operation (CCL operation))
First composite copper foil present embodiment being related to is cut into prescribed level, such as the CCL(Copper Clad Laminate forming with the FPC base material laminating consisting of polyimide resin film etc., copper-clad plate).That is, by heat treated, the epoxy that makes to be arranged on substrate surface is that the bonding agents such as bonding agent solidify, and the alligatoring face of alligatoring copper coating etc. that makes to have composite copper foil is closely sealed and carry out bonding with base material.Heating-up temperature, time can suitably be selected according to the solidification temperature of bonding agent, base material etc., while for example can be at the more than 150 ℃ temperature below 400 ℃, more than 1 minute below 120 minutes, the pressure that applies below the above 3.0MPa of 0.5MPa fits.
As mentioned above, the heat resistance of the rolled copper foil that composite copper foil has, can adjust according to heating-up temperature at this moment.Therefore, thus make by final cold rolling process the rolled copper foil in the state of being heating and curing by above-mentioned heating softening and modified one-tenth recrystallization.That is to say, the CCL operation of the composite copper foil of fitting on base material doubles as the recrystallization annealing operation to the rolled copper foil of composite copper foil.
Thus, by making CCL operation double as recrystallization annealing operation, until composite copper foil is fitted in the operation of base material, can be at rolled copper foil process composite copper foil, the distortion such as the stretching in the time of can making to be difficult for occurring rolled copper foil to be fitted on base material, fold, bending under the curing state of the processing after final cold rolling process.
In addition, the softening of rolled copper foil as above demonstrates, and by recrystallization annealing operation, obtained modified rolled copper foil, had the rolled copper foil of recrystallization texture.Thus, can access the rolled copper foil of resistance to bend(ing) excellence.
On the other hand, the copper coating on rolled copper foil and alligatoring copper foil layer are fully thin not hinder the mode of the recrystallization of rolled copper foil to form.In addition, form operation S20 form by the copper coating by above-mentioned, copper coating itself becomes than the state that is easier to recrystallization.Therefore think, in this recrystallization annealing operation, there is recrystallization at least a portion of copper coating together with rolled copper foil.
By upper, can improve the resistance to bend(ing) as composite copper foil integral body.
(Surface Machining operation)
Then, to fitting in the composite copper foil of base material, implement Surface Machining operation.In Surface Machining operation, composite copper foil is carried out forming operation, in order to improve the connection reliability of distribution and other electronic component, implementing the surface-treated surface treatment procedures such as plating processing and in order to protect distribution etc. to form the diaphragm formation operation of the diaphragms such as anti-solder flux to cover the mode of the part on distribution such as the distribution that uses the methods such as etching to form distribution (wire) etc.
By upper, manufacture the FPC used the composite copper foil that present embodiment relates to.
At this moment, because use has the composite copper foil of copper coating and alligatoring copper coating, wherein copper coating is the copper coating with afore mentioned rules state, and alligatoring copper coating is to omit as bottom, alligatoring the alligatoring copper coating reducing; Therefore the base material, exposing in FPC is in maintaining the state of high transmission rate.Therefore, obtain border observability excellence, the easy FPC of contraposition of distribution.
Other embodiment of the present invention
Above embodiments of the present invention are illustrated, but the present invention is not limited to above-mentioned embodiment, in the scope that does not depart from its aim, can has various changes.
For example, in the above-described embodiment, on copper coating, adhere to alligatoring grain and form alligatoring copper coating, but also can, in the formation operation of alligatoring copper coating, further carry out the processing of capsule plating.Thus, by capsule copper coating is so-called, by coating, covered alligatoring grain, can make alligatoring grain be grown to knot shape projection, can suppress coming off of alligatoring grain in addition.But, in the situation that want to retain alligatoring grain with fine state, do not need capsule copper plating treatment.
In addition, in the above-described embodiment, the CCL operation in FPC manufacturing process doubles as the recrystallization annealing operation to rolled copper foil, but recrystallization annealing operation also can be used as the operation different from CCL operation, carries out.
In addition, in the above-described embodiment, via bonding agent, carry out the laminating of composite copper foil and base material and manufacture 3 layer material CCL, but also can via bonding agent, directly not fit and manufacture 2 layer material CCL.In the situation that not using bonding agent, can make composite copper foil and the direct crimping of base material by heating, pressurization.The in the situation that of 2 layers of CCL, while can for example more than 150 ℃ at the temperature below 400 ℃, more than 1 minute below 30 minutes, the pressure that applies below the above 10MPa of 1MPa fits.
In addition, in the above-described embodiment, composite copper foil can be used for FPC purposes, but the purposes of composite copper foil is not limited to this, such as also can be for other purposes such as antenna of the negative pole current collection Copper Foil of lithium rechargeable battery, used for plasma display electromagnetic wave shield, IC-card.
In addition, in the above-described embodiment, as formation, there is the method for the copper coating of specified states as above, in the electrolysis plating etc. of organic system additive that has used regulation, found the effect of regulation.But, in addition, also can use the additive that can realize with the organic system additive same effect of afore mentioned rules.Or the formation operation by from above-mentioned other different copper coating, also can form the copper coating with rated condition as above.
The main starting point of the present invention is the alligatoring omission aspect that is to reduce alligatoring copper coating all the time.Also be in addition, as realizing this formation, the copper coating of composite copper foil is specified states, and the surperficial recess that particularly can be present in copper coating is the aspect below the size of regulation, and copper coating is configured to and can carries out by above-mentioned recrystallization annealing operation the aspect of recrystallization.
[embodiment]
Then, embodiments of the invention and comparative example are described simultaneously.
(1) with the making of rolled copper foil and the alligatoring paper tinsel of copper coating
In order to carry out various evaluations, make the rolled copper foil with copper coating and alligatoring paper tinsel that embodiment 1～9 and comparative example 1～11 relate to.
(embodiment 1)
First, the rolled copper foil with copper coating embodiment 1 being related to and alligatoring paper tinsel manufacturing process are carried out following explanation.
As former paper tinsel, using the thickness consisting of tough pitch copper (TPC) is the rolled copper foil of 11 μ m.In addition, use laser microscope to random 10 points of measuring in the surface of this rolled copper foil, the mean value of the degree of depth of surface voids is 0.7 μ m.
Then, implement electrolytic degreasing and pickling processes and the surface clean of rolled copper foil is clean.As electrolytic degreasing, in the aqueous solution that comprises 40g/L NaOH, 20g/L sodium carbonate, 40 ℃ of liquid temperatures, current density 10A/dm 2setting under carry out the processing in 10 seconds.After rolled copper foil is washed, as pickling, in comprising 150g/L sulphur aqueous acid, at 25 ℃ of liquid temperatures, flooded for 10 seconds.Afterwards, further rolled copper foil is washed.
Then form the copper coating of thickness 0.1 μ m.In this operation, used contain 170g/L copper sulfate pentahydrate, 70g/L sulfuric acid, as two (3-sulfonic acid propyl group) disulphide (SPS) powder reagents of the 30mg/L of organosulfur compound, as the Macrogol 3000 (polyethylene glycol that molal weight is 3000g/mol) of the 200mg/L of surfactant, as the CU-BRITETH-RIII-C of Co., Ltd. of Ren Yuanyou Gilat system of the 5ml/L of levelling agent, as the aqueous solution of the hydrochloric acid (the HCl aqueous solution) of the 0.15ml/L of chloride ion.As plating condition, at 35 ℃ of liquid temperatures, current density 7A/dm 2setting under carried out for 10 seconds.Afterwards, rolled copper foil is washed.
By upper, make the rolled copper foil with copper coating of embodiment 1.
Then, on copper coating, form alligatoring grain and form alligatoring copper coating.
First, form the alligatoring copper coating that is equivalent to 0.05 μ m thickness while flattening equably.In this operation, use the aqueous solution that contains 100g/L copper sulfate pentahydrate, 70g/L sulfuric acid, 20g/L ferric sulfate heptahydrate.As plating condition, at 30 ℃ of liquid temperatures, current density 60A/dm 2setting under carried out for 0.5 second.Afterwards, rolled copper foil is washed.
Then, on alligatoring copper coating, form successively nickel coating, zinc coating, chromaking processing layer, silane coupled processing layer and form antirust coat.
First, form the nickel coating of thickness 20nm.In this operation, used and contained 300g/L nickel sulfate hexahydrate compound, 45g/L nickel chloride, 50g/L boron aqueous acid.As plating condition, at 50 ℃ of liquid temperatures, current density 2A/dm 2setting under carried out for 5 seconds.Afterwards, rolled copper foil is washed.
Then, form the zinc coating of thickness 7nm.In this operation, used the aqueous solution that contains 90g/L zinc sulfate, 70g/L sodium sulphate.As plating condition, at 30 ℃ of liquid temperatures, current density 1.5A/dm 2setting under carried out for 4 seconds.Afterwards, rolled copper foil is washed.
Then, carry out 3 valency chromium chemical syntheses and process the chromaking processing layer that forms thickness 5nm.Afterwards, in containing the silane coupling solution of 5% 3-TSL 8330, at 25 ℃, flood after 5 seconds, at the temperature of 200 ℃, be dried at once, form silane coupled processing layer.
Forming the face of above-mentioned each layer, that is to say, in the face with the face opposite side of polyimide resin film laminating afterwards, do not form each layer as above, a part that similarly forms antirust coat by the method with above-mentioned and step, that is to say, nickel coating, zinc coating and chromaking processing layer.
By upper, make the alligatoring paper tinsel that embodiment 1 relates to.
(embodiment 2～9)
Then, make the rolled copper foil with copper coating and the alligatoring paper tinsel that embodiment 2～9 relates to.
The rolled copper foil with copper coating relating to about embodiment 2,3 except the thickness of copper coating is respectively 0.3 μ m, 0.6 μ m, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel that embodiment 2,3 relates to is made under the condition identical with the above embodiments 1.
The rolled copper foil with copper coating relating to about embodiment 4 is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel that embodiment 4 relates to, thus the thickness that is equivalent to 0.11 μ m while making alligatoring copper coating flatten equably forms large alligatoring grain, in addition, under the condition identical with the above embodiments 1, makes.
The rolled copper foil with copper coating relating to about embodiment 5,6 except the thickness of copper coating is respectively 0.3 μ m, 0.6 μ m, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel that embodiment 5,6 relates to is made under the condition identical with the above embodiments 4.
The rolled copper foil with copper coating relating to about embodiment 7 is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel relating to about embodiment 7, thus the thickness that is equivalent to 0.25 μ m while making alligatoring copper coating flatten equably forms large alligatoring grain, in addition, under the condition identical with the above embodiments 1, makes.
The rolled copper foil with copper coating relating to about embodiment 8,9 except the thickness of copper coating is respectively 0.3 μ m, 0.6 μ m, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel that embodiment 8,9 relates to is made under the condition identical with the above embodiments 7.
(comparative example 1～11)
Then, the rolled copper foil with copper coating of comparison example 1～11 and alligatoring paper tinsel.
The rolled copper foil with copper coating relating to about comparative example 1 is made under the condition identical with the above embodiments 2.In addition, the alligatoring paper tinsel relating to about comparative example 1, thus the thickness that is equivalent to 0.03 μ m while making alligatoring copper coating flatten equably forms little alligatoring grain, in addition, under the condition identical with the above embodiments 1, makes.
In the rolled copper foil with copper coating of comparative example 2, do not add organic system additive and carry out the formation of copper coating, in addition, under the condition identical with the above embodiments 2, make.In addition, the alligatoring paper tinsel relating to about comparative example 2 is made under the identical condition of the comparative example 1 with above-mentioned.
The rolled copper foil with copper coating relating to about comparative example 3 is made under the condition identical with the above embodiments 2.In addition, about comparative example 3 relate to alligatoring paper tinsel, use the plating solution that does not contain ferric sulfate heptahydrate to carry out the formation of alligatoring copper coating, in addition, under the identical condition of the comparative example 1 with above-mentioned, make.
The rolled copper foil with copper coating relating to about comparative example 4 except not forming copper coating, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel relating to about comparative example 4 is made under the identical condition of the comparative example 3 with above-mentioned.
The rolled copper foil with copper coating relating to about comparative example 5 is made under the condition identical with the above embodiments 2.In addition, the alligatoring paper tinsel relating to about comparative example 5, thus the thickness that is equivalent to 0.35 μ m while making alligatoring copper coating flatten equably forms large alligatoring grain, in addition, under the condition identical with the above embodiments 1, makes.
In the rolled copper foil with copper coating relating at comparative example 6, do not add organic system additive and carry out the formation of copper coating, in addition, under the condition identical with the above embodiments 2, making.In addition, the alligatoring paper tinsel relating to about comparative example 6 is made under the identical condition of the comparative example 5 with above-mentioned.
The rolled copper foil with copper coating relating to about comparative example 7 is made under the condition identical with the above embodiments 2.In addition, the alligatoring paper tinsel relating to about comparative example 7, is used the plating solution that does not contain ferric sulfate heptahydrate to carry out the formation of alligatoring copper coating, in addition, under the identical condition of the comparative example 5 with above-mentioned, makes.
The rolled copper foil with copper coating relating to about comparative example 8 except not forming copper coating, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel relating to about comparative example 8 is made under the identical condition of the comparative example 5 with above-mentioned.
In the rolled copper foil with copper coating relating at comparative example 9, do not add organic system additive and carry out the formation of copper coating, in addition, under the condition identical with the above embodiments 2, making.In addition, the alligatoring paper tinsel relating to about comparative example 9 is made under the condition identical with the above embodiments 4.
In the rolled copper foil with copper coating relating at comparative example 10, under the condition identical with the above embodiments 2, make.In addition, the alligatoring paper tinsel relating to about comparative example 10, is used the plating solution that does not contain ferric sulfate heptahydrate to carry out the formation of alligatoring copper coating, in addition, under the condition identical with the above embodiments 4, makes.
The rolled copper foil with copper coating relating to about comparative example 11 except not forming copper coating, is made under the condition identical with the above embodiments 1.In addition, the alligatoring paper tinsel relating to about comparative example 11 is made under the condition identical with the above embodiments 4.
(2) with the evaluation of rolled copper foil and the alligatoring paper tinsel of copper coating
The rolled copper foil with copper coating and alligatoring paper tinsel that the embodiment 1～9 making as mentioned above and comparative example 1～11 are related to, carry out following evaluation.
(surface roughness measurement)
Carry out the surface roughness measurement of the rolled copper foil with copper coating that embodiment 1～9 and comparative example 1～11 relate to.
About surface roughness measurement with the rolled copper foil of copper coating to each, use laser microscope, the recess depths that the copper coating surface existing in the visual field 500 times of multiplying powers is existed is measured.In the mensuration of every 1 time, using part the highest in the measured length of the approximately 200 μ m that select at random as datum mark, for the recess existing in this measured length, measure to be recessed into which kind of degree from datum mark.By its 5 times repeatedly, using the degree of depth of the aggregate value of the degree of depth of recess recess in this copper coating divided by the value of the number of recess.
(particle size determination of alligatoring grain)
The particle diameter of the alligatoring grain that the alligatoring paper tinsel that mensuration embodiment 1～9 and comparative example 1～11 relate to has.
Use SEM observes the alligatoring face of each alligatoring paper tinsel, measures at random the particle diameter of 100 alligatoring grains.Then obtain this average grain diameter of 100.In addition, the poor ratio of the particle diameter of the maximum particle diameter in these 100 and minimum grain size is calculated by following formula.
Ratio (%)=(1-minimum grain size/maximum particle diameter) * 100 that particle diameter is poor.
Each numerical value of obtaining is thus the value that comprises antirust coat, but because antirust coat is thin fully, so its impact can be ignored.
(area estimation that alligatoring is omitted)
Measure alligatoring grain in the alligatoring face of the alligatoring paper tinsel that embodiment 1～9 and comparative example 1～11 relate to without growth part, be the area of alligatoring holiday.
Use SEM under 10,000 times of multiplying powers, to observe the alligatoring face of each alligatoring paper tinsel, part to alligatoring grain unconfirmed is judged to be and produces the part that alligatoring is omitted, by the image of SEM, obtained the area of alligatoring holiday, obtain the summation that area is omitted in the alligatoring in the visual field of 10,000 times of multiplying powers.
In addition, at this moment, only for reference, also carry out the observation in each alligatoring paper tinsel cross section.That is, for using the ion milling device of Hitachi's system to observe by SEM from the cross section of each alligatoring paper tinsel with rolling direction perpendicular cuts.
(mensuration of PI light transmittance)
Mensuration is fitted with the light transmission rate in polyimides (PI) resin molding of the alligatoring paper tinsel that embodiment 1～9 and comparative example 1～11 relate to.
First, by vacuum press, under 300 ℃ of temperature, pressure 5MPa, the condition of 15 minutes, the alligatoring face of each alligatoring paper tinsel is fitted in to the two sides of polyimide resin film.What at this moment use is the thick polyimide resin film of PIKUSHIO50 μ m of the Kaneka of Co., Ltd. system.The size of polyimide resin film and alligatoring paper tinsel is vertical 100mm * horizontal 60mm.Condition about laminating, is set as giving the heat (just can make crystallization recrystallize fully and obtain the heat of high bendability) that makes the full annealing of alligatoring paper tinsel and have annealing characteristic, and meets the recommendation condition of polyimide resin film manufacturer.
Then, to being fitted in each alligatoring paper tinsel of polyimide resin film, by the injection etching of iron chloride, process.Thus, the alligatoring paper tinsel on polyimide resin film two sides is removed completely, the polyimide resin film of bottom becomes the state that all expose on two sides.
To the polyimide resin film exposing, use the spectrophotometer UV-1800 of Shimadzu Seisakusho Ltd.'s system to be determined at the light transmission rate in wavelength 700nm.The wavelength of the CCD camera using during due to FPC actual installation is generally 500nm～800nm, therefore selects 700nm as tested wavelength.The light transmission rate of wavelength 700nm is preferably more than 50%.
(gap of Copper Foil/PI is measured)
Mensuration is fitted with the polyimide resin film of alligatoring paper tinsel and the gap of alligatoring paper tinsel that embodiment 1～9 and comparative example 1～11 relate to.
Under condition same as described above, each alligatoring paper tinsel is fitted in to the two sides of polyimide resin film, to using the cross section of the ion milling device cutting of Hitachi's system to observe by SEM.Between observation width 200 μ m in an optional side's binding face, under 10,000 times of multiplying powers, the number in visible large gap is counted.The number in gap is preferably below 2.
(mensuration of peel strength)
Mensuration is fitted with the peel strength of the alligatoring paper tinsel in the polyimide resin film of the alligatoring paper tinsel that embodiment 1～9 and comparative example 1～11 relate to, and evaluates the adaptation of alligatoring paper tinsel and polyimide resin film.According to assay method below, peel strength more high adhesion is higher.
That is,, under condition same as described above, each alligatoring paper tinsel is fitted in to the two sides of polyimide resin film.Then, in a side binding face, at the masking tape of the upper surface laminating width 1mm of the rolled copper foil side of alligatoring paper tinsel, in the opposing party's binding face, at whole laminating masking tape of rolled copper foil.In this state, by the injection etching of iron chloride, process.Thus, at a side binding face, utilize masking tape that the alligatoring paper tinsel beyond crested region is removed, become the state that the polyimide resin film of bottom exposes.By masking tape, protecting the opposing party's of whole face side, is the not etched and residual state of alligatoring paper tinsel.
By being fitted with the polyimide resin film that alligatoring paper tinsel, a part expose, in 3% dilute sulfuric acid of 50 ℃, flood 1 hour, measure the peel strength before and after dipping.In this is measured, to the alligatoring paper tinsel of etched 1mm width from polyimide resin film take 90 ° of angles while peeling off needed masterpiece measure as peel strength.In addition, the peel strength of calculating (sulfuric acid dipping) after dipping with respect to dipping before the ratio (%) of peel strength of (normality), evaluate medicine durability, i.e. the rear peel strength of dipping which kind of degree that declined.More than peel strength under normality is preferably 1.0N/nm, medicine durability is preferably more than 80%.
(evaluation of border observability)
Evaluation is fitted with the border observability of the alligatoring paper tinsel in the polyimide resin film of alligatoring paper tinsel of embodiment 1～9 and comparative example 1～11.
Under condition same as described above, each alligatoring paper tinsel is fitted in to the two sides of polyimide resin film.Then,, at a side binding face, the masking tape at the upper surface laminating width 1mm of the rolled copper foil side of alligatoring paper tinsel, at the opposing party's binding face, shows out the whole of rolled copper foil.In this state, by the injection etching of iron chloride, process.Thus, at a side binding face, utilize masking tape that the alligatoring paper tinsel beyond crested region is removed, become the state that the polyimide resin film of bottom exposes.In the opposing party's face side, alligatoring paper tinsel is removed completely, becomes the whole state of showing out of polyimide resin film of bottom.
Using alligatoring paper tinsel side etched and that become 1mm width as the back side, use the whole side of showing out of metal microstructure sem observation polyimide resin film.Thus, when seeing through polyimide resin film and observing, evaluate the alligatoring paper tinsel that becomes 1mm width end, be the observability on the border of alligatoring paper tinsel and polyimide resin film.Using by the visual deep or light judgment standard that can contraposition by CCD camera during as FPC actual installation that whether can confirm clearly border.Can confirm clearly to be designated as judgement (〇), can not confirm to be designated as undecidable (*).
In addition, the judgment standard isotactic in above evaluation is decided to be the roughly benchmark that quality in the present embodiment is judged, according to the alligatoring paper tinsel as actual product, the form of FPC, desired purposes etc., can suitable change the scope of each suitability in evaluating.
(3) with the evaluation result of rolled copper foil and the alligatoring paper tinsel of copper coating
The rolled copper foil with copper coating that embodiment 1～9 and comparative example 1～11 are related to and each evaluation result of alligatoring paper tinsel are shown in following table 1.
[table 1]
As shown in table 1, the arbitrary numerical value in the rolled copper foil with copper coating that embodiment 1～9 relates to and alligatoring paper tinsel is all in above-mentioned scope.On the other hand, the rolled copper foil with copper coating that comparative example 1～11 relates to and the arbitrary numerical value in alligatoring paper tinsel is not all in above-mentioned scope.In the alligatoring paper tinsel relating at comparative example 9, although the poor ratio of the average grain diameter of alligatoring grain, particle diameter in prescribed limit, alligatoring is omitted, the gap with polyimide resin film, medicine durability, border vision intensity any all not in prescribed limit.Think that this is because do not add organic system additive in the plating solution of the copper coating of the bottom as alligatoring copper coating.
Find in addition, the recess in copper coating is darker, or the average grain diameter of the alligatoring grain that has of alligatoring copper coating is less, and area is omitted in alligatoring the tendency that becomes large.
Find in addition, the average grain diameter of the alligatoring grain that alligatoring copper coating has is larger, and the light transmittance of polyimide resin film has the tendency of reduction.
Find in addition, the poor ratio of the particle diameter of the alligatoring grain that alligatoring copper coating has is larger, or alligatoring to omit area larger, the number in the gap of alligatoring paper tinsel and polyimide resin film has the tendency more than becoming.
Find in addition, the average grain diameter of the alligatoring grain that alligatoring copper coating has is less, and the peel strength under normality has the tendency of reduction.Find in addition, the number in the gap of alligatoring paper tinsel and polyimide resin film more increases, and medicine durability has the tendency of reduction.
Find in addition, the average grain diameter of the alligatoring grain that alligatoring copper coating has is larger, or the number in the gap of alligatoring paper tinsel and polyimide resin film more increases, and the border observability of alligatoring paper tinsel has the tendency of reduction.
(by the observed result of SEM)
Fig. 2, Fig. 3 represent the surface of passing through SEM of the alligatoring paper tinsel that embodiment 8 and comparative example 4 relate to and the observed result of section.The upper semisection of Fig. 2 is that embodiment 8, lower semisection are comparative example 4.In addition, in the surface observation of Fig. 2, respectively alligatoring paper tinsel is got the SEM image of different multiplying.Wherein, the area that the alligatoring of above-mentioned table 1 is omitted is that the SEM photo based on 10,000 times of central multiplying powers is calculated.
In the embodiment 8 shown in the upper semisection of Fig. 2, the surface integral of copper coating is roughened grain and covers, and in the visual field in these SEM images, does not confirm alligatoring and omits.On the other hand, known in the comparative example 4 shown in the lower semisection of Fig. 2, the part that exists the copper coating of the emboliform profile do not confirm from alligatoring grain, bottom to expose.This be alligatoring grain without growth part, i.e. alligatoring holiday.
In addition, Fig. 3 represents the SEM image of the section of these alligatoring paper tinsels.In the embodiment 8 in Fig. 3 left side, alligatoring grain becomes at predetermined distance connected state interruptedly not, and the SEM image by section does not confirm alligatoring yet and omits.On the other hand, in the comparative example 4 on Fig. 3 right side, alligatoring grain interrupts copper coating is exposed for a part, and the SEM image by section also confirms and produced alligatoring omission.

Claims (8)

1. a composite copper foil, is characterized in that, has:
Rolled copper foil,
The copper coating forming at least one side of described rolled copper foil, and
What on described copper coating, form comprises the alligatoring copper coating that average grain diameter is more than 0.05 μ m alligatoring grain below 0.30 μ m;
The poor ratio of the maximum particle diameter of described alligatoring grain and the particle diameter of minimum grain size is below 65%,
The cross section that described alligatoring copper coating is blocked from thickness direction, form following state: the described alligatoring grain continuously distance more than 20 μ m does not interrupt and is connected on described copper coating,
Wherein, poor percentage=(1-minimum grain size/maximum particle diameter) * 100 of particle diameter.
2. a composite copper foil, is characterized in that, has:
Rolled copper foil,
The copper coating forming at least one side of described rolled copper foil, and
What on described copper coating, form comprises the alligatoring copper coating that average grain diameter is more than 0.05 μ m alligatoring grain below 0.30 μ m;
The poor ratio of the maximum particle diameter of described alligatoring grain and the particle diameter of minimum grain size is below 65%,
Utilize scanning electron microscope, the area without forming section of the described alligatoring grain existing in the visual field of 10,000 times of multiplying powers is 5 μ m 2below.
Wherein, poor percentage=(1-minimum grain size/maximum particle diameter) * 100 of particle diameter.
3. composite copper foil according to claim 1 and 2, is characterized in that,
In the situation that the surface of described copper coating exists recess, the mean value of the degree of depth of described recess is below 0.60 μ m.
4. according to the composite copper foil described in any one in claim 1～3, it is characterized in that,
Described copper coating use has been added the copper electrolyte of organosulfur compound, surfactant, levelling agent and the chloride ion with sulfydryl and has formed.
5. according to the composite copper foil described in any one in claim 1～4, it is characterized in that,
When described alligatoring copper coating is flattened equably, be equivalent to the thickness below the above 0.25 μ m of 0.05 μ m.
6. according to the composite copper foil described in any one in claim 1～5, it is characterized in that,
On described alligatoring copper coating, having thickness is the antirust coat below the above 70nm of 11nm.
7. according to the composite copper foil described in any one in claim 1～6, it is characterized in that,
On described alligatoring copper coating, be formed with successively nickel coating, zinc coating, chromaking processing layer and silane coupled processing layer, and to have thickness be the antirust coat below the above 70nm of 11nm.
8. a manufacture method for composite copper foil, is characterized in that, has:
On at least one side of rolled copper foil, form the operation of copper coating, and
On described copper coating, form and comprise the operation that average grain diameter is more than 0.05 μ m alligatoring copper coating of the alligatoring grain below 0.30 μ m;
In forming the operation of described copper coating,
With the copper electrolyte that has added organosulfur compound, surfactant, levelling agent and the chloride ion with sulfydryl, form described copper coating.
CN201410025355.6A 2013-02-06 2014-01-20 Composite Copper Foil And Manufacturing Method Therefor Pending CN103963376A (en)

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