CN104010810A - Copper-foil composite, formed body, and manufacturing method therefor - Google Patents

Copper-foil composite, formed body, and manufacturing method therefor Download PDF

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Publication number
CN104010810A
CN104010810A CN201380004621.0A CN201380004621A CN104010810A CN 104010810 A CN104010810 A CN 104010810A CN 201380004621 A CN201380004621 A CN 201380004621A CN 104010810 A CN104010810 A CN 104010810A
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CN
China
Prior art keywords
copper foil
resin bed
layer
foil composite
composite
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CN201380004621.0A
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CN104010810B (en
Inventor
田中幸一郎
冠和树
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Structure Of Printed Boards (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

[Problem] To provide the following: an easily workable copper-foil composite wherein a copper foil is prevented from breaking even if subjected to a demanding (complex) deformation that differs from single-axis bending (such as press forming); a formed body; and a manufacturing method therefor. [Solution] A copper-foil composite comprising a copper foil and a resin layer laminated to each other. The thickness (t2, in mm) of the copper foil, the stress (f2, in MPa) in the copper foil at a tensile strain of 4%, the thickness (t3, in mm) of the resin layer, and the stress (f3, in MPa) in the resin layer at a tensile strain of 4% satisfy formula 1: (f3t3)/(f2t2) >= 1. The 180 DEG peel adhesion strength (f1, in N/mm) between the copper foil and the resin layer, the strength (F, in MPa) of the copper-foil composite at a tensile strain of 30%, and the thickness (T, in mm) of the copper-foil composite satisfy formula 2: 1 <= 33f1/(FT). A nickel layer and/or nickel-alloy layer with a total thickness of 0.001-5.0 [mu]m are/is formed on the surface of the copper foil to which the resin layer is not laminated.

Description

Copper foil composite and formed body and manufacture method thereof
Technical field
The invention relates to copper foil composite and formed body and manufacture method thereof that a kind of laminated copper foil and resin bed form.
Background technology
The copper foil composite that laminated copper foil and resin bed form is applied to FPC(flexible print wiring board), electromagnetic shielding material, RF-ID(Wireless IC tag), planar heat producing body and radiator etc.For example, the in the situation that of FPC, form the circuit of Copper Foil on base resin layer, the covering layer film of holding circuit covers circuit, and becomes the stepped construction of resin bed/Copper Foil/resin bed.
Therefore, the processability of such copper foil composite requires the bending taking MIT bendability as representative, the high reversed bending taking IPC bendability as representative, has proposed the copper foil composite (for example, patent documentation 1～3) of bending property or bendability excellence.For example, FPC can bend at movable parts such as the hinge parts of mobile phone, or bends use for seeking the little spatialization of circuit, but as deformation pattern, taking above-mentioned MIT bend test or IPC bend test as the such single shaft bending of representative, and the mode that does not become harsh deformation pattern designs.
In addition, copper foil composite for electromagnetic shielding material etc. in the situation that, is become to the stepped construction of resin bed/Copper Foil, require surface performance corrosion resistance and the electric contact performance steady in a long-term of such copper foil composite.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2010-100887 communique
Patent documentation 2: TOHKEMY 2009-111203 communique
Patent documentation 3: TOHKEMY 2007-207812 communique.
Summary of the invention
The problem that invention will solve
But, if above-mentioned copper foil composite is carried out to press process etc., become the deformation pattern of harsh (complexity) different from MIT bend test or IPC bend test, thereby have the problem of Copper Foil fracture.And, as long as can carry out press process to copper foil composite, can make the structure that contains circuit meet article shape.
Therefore, even if the object of the present invention is to provide a kind of carry out such harsh (complexity) of being different from single shaft bending such as press process thus distortion also can prevent Copper Foil break copper foil composite and formed body and the manufacture method thereof of excellent in workability and then long-time stable performance corrosion resistance and electric contact performance.
The technological means of dealing with problems
The discoveries such as the inventor, by the deformational behavior of resin bed is passed to Copper Foil, are out of shape Copper Foil and resin bed in the same manner, thereby make the contraction of Copper Foil be difficult for producing and improving ductility, can prevent that Copper Foil from breaking, thereby complete the present invention.That is to say, the mode that is passed to Copper Foil with the deformational behavior of resin bed specifies the characteristic of resin bed and Copper Foil.And then, for long-time stable performance corrosion resistance and electric contact performance, and the coating of regulation copper foil surface.
That is, copper foil composite of the present invention is laminated with Copper Foil and resin bed, and the thickness of above-mentioned Copper Foil is being made as to t 2(mm) stress of the above-mentioned Copper Foil during, by elongation strain 4% is made as f 2(MPa), the thickness of above-mentioned resin bed is made as to t 3(mm) stress of the above-mentioned resin bed during, by elongation strain 4% is made as f 3(MPa), time, meet formula 1:(f 3× t 3)/(f 2× t 2)>=1, and be made as f peeling off adhesive strength by 180 ° of above-mentioned Copper Foil and above-mentioned resin bed 1(N/mm), the intensity during by the elongation strain 30% of above-mentioned copper foil composite is made as F(MPa), the thickness of above-mentioned copper foil composite is made as to T(mm) time, meet formula 2:1≤33f 1/ (F × T); The face that is not laminated with above-mentioned resin bed in above-mentioned Copper Foil, is formed with the Ni layer and/or the Ni alloy-layer that amount to thickness 0.001～5.0 μ m.
Preferably the total thickness of this Ni layer and/or Ni alloy-layer is 0.001～0.50 μ m.
Preferably, at the temperature of the glass transition temperature lower than above-mentioned resin bed, above-mentioned formula 1 and formula 2 are set up.
The tension failure strain l of preferred above-mentioned copper foil composite and the ratio l/L of the tension failure strain L of above-mentioned resin bed monomer are 0.7～1.
Formed body of the present invention is that above-mentioned metal forming complex is processed.Formed body of the present invention for example can be by carrying out press process, use and have other processing of outstanding processing, the drawing of upper/lower die processing etc. three-dimensionally to process.
The manufacture method of formed body of the present invention is that above-mentioned metal forming complex is processed.
Invention effect
According to the present invention, the copper foil composite of excellent in workability and then long-time stable performance corrosion resistance and electric contact performance even if can obtain that a kind of distortion of carrying out press process such harsh (complexity) that be different from single shaft bending also can prevent that Copper Foil from breaking.
Brief description of the drawings
Fig. 1 is that experimentally represents f 1figure with the relation of (F × T).
Fig. 2 is the figure that represents the formation of the AEG-process device of the evaluation of carrying out processability.
Detailed description of the invention
Copper foil composite of the present invention is laminated copper foil and resin bed and form.Copper foil composite of the present invention for example can be applicable to FPC(flexible print wiring board), electromagnetic shielding material, RF-ID(Wireless IC tag), planar heat producing body and radiator, but be not limited to these.
< Copper Foil >
The thickness t of Copper Foil 2be preferably 0.004～0.05mm(4～50 μ m).If t 2lower than 0.004mm(4 μ m), the ductility of Copper Foil significantly reduces and the processability of copper foil composite is not improved sometimes.Copper Foil preferably has more than 4% tension failure strain.If t 2exceed 0.05mm(50 μ m), in the time making copper foil composite, the impact of the characteristic of Copper Foil monomer manifests significantly and the processability of copper foil composite is not improved sometimes.
As Copper Foil, the Copper Foil of can use rolled copper foil, electrolytic copper foil, realizing by metallizing etc., make excellent in workability, can reduce intensity (f but be preferably by recrystallization simultaneously 2) rolled copper foil.Be formed with for bonding, antirust processing layer at copper foil surface, also these be included in Copper Foil and pay attention to.
< resin bed >
As resin bed, there is no particular restriction, resin material can be coated to Copper Foil and formed resin bed, but be preferably the resin molding that can be attached at Copper Foil.As resin molding, can enumerate PET(PET) film, PEN(PEN), PI(polyimides) film, LCP(liquid crystal polymer) film and PP(polypropylene) film.
As the laminating method of resin molding and Copper Foil, can between resin molding and Copper Foil, use bonding agent, also resin molding hot pressing can be connected to Copper Foil.In addition, if the intensity of bond layer is low, be difficult to improve the processability of copper foil composite, therefore the intensity of bond layer is preferably the stress (f of resin bed 3) more than 1/3.Its reason is: in the present invention, by " deformational behavior of resin bed is passed to Copper Foil; Copper Foil is also out of shape in the same manner with resin bed; thereby make the contraction of Copper Foil be difficult for producing and improving ductility " as technological thought, if the intensity of bond layer is low, relax to some extent in the distortion of bond layer, and the behavior of resin can not be passed to Copper Foil.
It should be noted that, in the situation that using bonding agent, the characteristic of following resin bed is so that bond layer and resin bed merge the person of forming for object.
The thickness t of resin bed 3be preferably 0.012～0.12mm(12～120 μ m).If t 3lower than 0.012mm(12 μ m), (f sometimes 3× t 3)/(f 2× t 2) < 1.If t 3be thicker than 0.12mm(120 μ m), the flexibility of resin bed (flexible) reduce and rigidity becomes too high, processability is deteriorated.Resin bed is preferably the tension failure strain having more than 40%.
< copper foil composite >
The combination of the copper foil composite forming as stacked above-mentioned Copper Foil and resin bed, can enumerate the double-decker of Copper Foil/resin bed or the 3-tier architecture of Copper Foil/resin bed/Copper Foil.There is Copper Foil (Copper Foil/resin bed/Copper Foil) (the f of entirety in the both sides of resin bed 2× t 2) value be made as will 2 layers of Copper Foil be calculated separately and each (f 2× t 2) value be added and the value that obtains.
180 ° of < peel off adhesive strength >
Copper Foil is because its thin thickness is easily in thickness direction generation contraction.Shrink if produce, Copper Foil fracture, thereby ductility reduces.On the other hand, resin bed has the feature (region of homogeneous strain is wide) that is difficult for producing contraction in the time stretching.Therefore, in the complex of Copper Foil and resin bed, by the deformational behavior of resin bed is passed to Copper Foil, Copper Foil is also out of shape in the same manner with resin, shrinks thereby make Copper Foil be difficult for producing, and improve ductility.Now, if the adhesive strength of Copper Foil and resin bed is low, the deformational behavior of resin bed cannot be passed to Copper Foil, and ductility does not improve (peel off and copper is broken).
Therefore, must improve adhesive strength.As adhesive strength, shear bond power is considered to direct index, if but improve adhesive strength, the intensity that makes shear bond power and copper foil composite is peer-level, rupture in the position except bonding plane, thereby become and be difficult to measure.
According to such situation, use in the present invention 180 ° to peel off adhesive strength f 1value.Shear bond strength is completely different from 180 ° of absolute values of peeling off adhesive strength, but processability or tensile elongation, and 180 ° peel off between adhesive strength visible associatedly, therefore peel off the index of adhesive strength as adhesive strength using 180 °.
Herein, in fact think " intensity=shearing closing force when fracture ", for example think in the case of as need more than 30% elongation strain, become " flow stress≤shearing closing force of 30% ", in the case of more than 50% elongation strain, becoming " flow stress≤shearing closing force of 50% " as needed.And according to inventor's etc. experiment, if elongation strain becomes more than 30%, processability becomes well, the intensity while therefore adopting elongation strain to be 30% as following is as the intensity F of copper foil composite.
Fig. 1 is that experimentally represents f 1with the figure of the relation of (F × T), by the f of following each embodiment and comparative example 1map with the value of (F × T).(F × T) is the power in the time of elongation strain 30%, copper foil composite being applied, if regarded as for processability is improved and required MIN shear bond strength, if f 1identical with the absolute value of (F × T), both meetings are visible associated in gradient 1.
But, in Fig. 1, be not the f of all data 1with (F × T) be identical associated, the f with respect to (F × T) of the poor each comparative example of processability 1coefficient correlation (that is to say, by the initial point of Fig. 1, with respect to the f of (F × T) 1gradient) less, 180 ° to peel off adhesive strength correspondingly poor.On the other hand, the gradient of each embodiment is greater than the gradient of each comparative example, the embodiment 18(of gradient minimum just in the time of strain 30% fracture example) gradient be 1/33, therefore this value is regarded as in order to improve the necessary MIN shear bond strength of processability and 180 ° of coefficient correlations of peeling off between adhesive strength., regard shear bond power as 180 ° and peel off adhesive strength f 133 times.
It should be noted that, the in the situation that of comparative example 3, the gradient of Fig. 1 exceedes 1/33, but following formula 1:(f 3× t 3)/(f 2× t 2) lower than 1, thereby processability is deteriorated.
Peel off the power that adhesive strength is per unit width (N/mm) for 180 °.
Be 3-tier architecture and while there is multiple bonding plane at copper foil composite, use 180 ° in each bonding plane to peel off the value that adhesive strength is minimum.Its reason is that the bonding plane of most fragile can peel off.
In addition, can change and make the pressure of Copper Foil and the stacked compound tense of resin bed or temperature conditions and improve adhesive strength.Be preferably the pressure, the temperature that in the scope of not damaging resin bed, increase when stacked simultaneously.
As the method for adhesive strength that improves Copper Foil and resin bed, can list by chromate processing etc. and at the copper foil surface (face of resin bed side, below be suitably called " bonding plane ") Cr oxide skin(coating) is set, or copper foil surface is implemented to roughening treatment, or at copper foil surface, Ni layer or Ni alloy-layer are set, or after copper foil surface coating Ni, Cr oxide skin(coating) are set.In addition, being opposition side with resin bed, copper foil surface (non-bonding plane) forms Ni layer or Ni alloy-layer as described as follows, also can with form this Ni layer or Ni alloy-layer at non-bonding plane in, also form Ni layer or Ni alloy-layer with same step at bonding plane.Further, also can form after Ni layer or Ni alloy-layer at bonding plane, form Cr oxide skin(coating).
The thickness of the Cr oxide skin(coating) of bonding plane side is preferably made as with Cr weight and counts 5～100 μ g/dm 2.This thickness can calculate according to the chromium content that utilizes wet analysis to obtain.In addition, the existence of Cr oxide skin(coating) can be judged (peak of Cr because of oxidation be offset) by whether utilizing x-ray photoelectron spectroscopy (XPS) to detect Cr.
The above-mentioned Ni layer of bonding plane side or the thickness of Ni alloy-layer are preferably made as 0.001～5.0 μ m.If the thickness of Ni layer or Ni alloy-layer exceedes 5.0 μ m, the ductility of Copper Foil (and copper foil composite) reduces sometimes.
In addition, can change and make the pressure of Copper Foil and the stacked compound tense of resin bed or temperature conditions and improve adhesive strength.Be preferably the pressure, the temperature that in the scope of not damaging resin bed, increase when stacked simultaneously.
The face that is not laminated with above-mentioned resin bed (non-bonding plane) in Copper Foil, is formed with in order to give long-time stable electric contact the Ni layer and/or the Ni alloy-layer that amount to thickness 0.001～5.0 μ m.If the total thickness of these layers, lower than 0.001 μ m, cannot obtain stable electric contact.The total thickness of these layers becomes the thicker stability that more can improve electric contact performance, even if but total thickness exceedes 5.0 μ m, and above-mentioned effect is also saturated.The total thickness of Ni layer and/or Ni alloy-layer is preferably 0.001～0.50 μ m, more preferably 0.005～0.10 μ m.
In addition, Ni alloy-layer is preferably following alloy: contain Ni more than 20wt%, and then contain more than one in the Zn, the Sn that amount to more than 5wt%, Co, Cr, Mn, V, P, B, W, Mo, Fe, remainder is inevitable impurity.
It should be noted that, can form at least one of above-mentioned Ni layer or Ni alloy-layer at the non-bonding plane of Copper Foil.In addition, form Ni layer and Ni alloy-layer both at the non-bonding plane of Copper Foil, can be the order for Ni layer/Ni alloy-layer from most surface, also can be the order for Ni alloy-layer/Ni layer from most surface.In addition, " total thickness " refers to the aggregate values of the thickness of Ni layer and the thickness of Ni alloy-layer.
＜（f 3×t 3）/（f 2×t 2）＞
Next, the ((f to claim 3× t 3)/(f 2× t 2)) meaning of (hereinafter referred to as " formula 1 ") describes.Copper foil composite is Copper Foil and the resin bed that is laminated with same widths (size), thereby formula 1 represents the ratio of the power that the Copper Foil of formation copper foil composite and resin bed are applied.Therefore, this is than being more than 1 to mean resin bed side is applied to more power, and the intensity of resin bed side is higher than Copper Foil.And Copper Foil does not rupture and represents good processability.
On the other hand, if become (f 3× t 3)/(f 2× t 2) < 1, be that Copper Foil side is applied to more power, thereby can not produce the above-mentioned effect of " deformational behavior of resin bed is passed to Copper Foil and Copper Foil is also out of shape in the same manner with resin ".
Herein, f 2and f 3for example, as long as for producing the stress under the same strain amount after plastic deformation, but consider the strain that the tension failure strain of Copper Foil and the plastic deformation of resin bed (PET film) start, and be made as the stress of elongation strain 4%.It should be noted that f 2and f 3(and f 1) be to be all made as MD(Machine Direction, value longitudinally).
＜33f 1/（F×T）＞
Next the, (33f to claim 1/ (F × T)) meaning of (hereinafter referred to as " formula 2 ") describes.As mentioned above, because being 180 °, the shear bond power of the adhesive strength of direct representation necessary MIN Copper Foil and resin bed in order to improve processability peels off adhesive strength f 1approximately 33 times, thereby 33f 1represent in order to improve the necessary MIN adhesive strength of processability of Copper Foil and resin bed.On the other hand, (F × T) is power that copper foil composite is applied, thereby formula 2 becomes the ratio of Copper Foil and the adhesive strength of resin bed and the enhanced stretch resistance of copper foil composite.And if copper foil composite is stretched, at the interface of Copper Foil and resin bed, the Copper Foil by wanting to carry out local deformation applies shear stress with the resin of the homogeneous strain of wanting to stretch.Therefore, if adhesive strength lower than this shear stress, copper and resin bed are peeled off, and the deformational behavior of resin bed cannot be passed to Copper Foil, thus the ductility of Copper Foil does not improve.
That is to say, if the ratio of formula 2 lower than 1, it is weak and Copper Foil and resin are become easily peel off that adhesive strength becomes the power that applies of comparison copper foil composite, Copper Foil ruptures because of the processing such as compressing.
If the ratio of formula 2 is more than 1, copper and resin bed are not peeled off and the deformational behavior of resin bed can be passed to Copper Foil, thereby the ductility of Copper Foil is improved.It should be noted that, the ratio of formula 2 is more high more preferred, but realizes more than 10 value difficulty comparatively conventionally, thereby is preferably the upper limit of formula 2 is made as to 10.
It should be noted that, think 33f 1/ (F × T) is larger, and processability more improves, but elongation strain l and the 33f of resin bed 1/ (F × T) is disproportionate.This is to be subject to (f 3× t 3)/(f 2× t 2) the impact of ductility of size, Copper Foil, resin bed monomer cause, but as long as for meeting 33f 1/ (F × T)>=1, (f 3× t 3)/(f 2× t 2the Copper Foil of)>=1 and the combination of resin bed, just can obtain the complex with required processability.
, use intensity when elongation strain 30% to be as the reason of the intensity F of copper foil composite herein, as mentioned above, if elongation strain becomes more than 30%, processability becomes good.In addition, its reason is, carry out the tension test of copper foil composite, result is until elongation strain 30%, can because of strain, to cause flow stress to produce larger poor, even if can not make flow stress produce larger poor (process a little and solidify, but the gradient of curve becomes quite little) by elongation strain after 30% yet.
It should be noted that, the elongation strain of copper foil composite is not, in more than 30% situation, the hot strength of copper foil composite to be made as to F.
As mentioned above, even if copper foil composite of the present invention is the distortion of carrying out press process such harsh (complexity) that be different from single shaft bending, also can prevents that Copper Foil from breaking, and make excellent in workability.Particularly the present invention is suitable for the solid forming as press process.By copper foil composite is carried out to solid forming, can make copper foil composite become complicated shape, maybe can make the intensity of copper foil composite improve, framework that for example also can be using copper foil composite itself as various power circuits, thus can seek the minimizing of part number of packages or cost.
＜l/L＞
The tension failure strain l of copper foil composite and the ratio l/L of the tension failure strain L of resin bed monomer are preferably 0.7～1.
Conventionally, the tension failure strain of resin bed is overwhelmingly higher than the tension failure strain of Copper Foil, and similarly, the breaking strain of resin bed monomer is overwhelmingly higher than the tension failure strain of copper foil composite.On the other hand, as mentioned above, in the present invention, the deformational behavior of resin bed is passed to Copper Foil and the ductility of Copper Foil is improved, follow in this, can make the tension failure strain of copper foil composite be increased to resin bed monomer tension failure strain 70～100%.And, if be that more than 0.7 press formability further improves than l/L.
It should be noted that, the tension failure strain l of copper foil composite is the tension failure strain while carrying out tension test, in the time that resin bed and Copper Foil rupture simultaneously, is made as this value, the value be made as Copper Foil fracture in the time that Copper Foil first ruptures time.
The Tg > of < resin bed
Conventionally, resin bed at high temperature strength decreased or bonding force reduces, thereby at high temperature becomes and be difficult to meet (f 3× t 3)/(f 2× t 2)>=1 or 1≤33f 1/ (F × T).For example,, at the Tg(of resin bed glass transition temperature) more than temperature under, sometimes become the intensity or the bonding force that are difficult to maintain resin bed, if lower than the temperature of Tg, have to become easily to maintain the intensity of resin bed or the tendency of bonding force.That is to say, if lower than the Tg(glass transition temperature of resin bed) temperature (for example 5 DEG C～215 DEG C), copper foil composite becomes and easily meets (f 3× t 3)/(f 2× t 2)>=1 and 1≤33f 1/ (F × T).It should be noted that, even if in the temperature lower than Tg, also think and have following tendency: when temperature is higher, the intensity of resin bed or closing force diminish, be difficult to meet formula 1 and the following embodiment 19-21 of formula 2(reference and become).
And then, distinguish, in the situation that meeting formula 1 and formula 2, even if for example, in the relatively high temperature (40 DEG C～215 DEG C) of the Tg lower than resin bed, also can maintain the ductility of copper foil composite.Even if if for example, also can maintain the ductility of copper foil composite in the relatively high temperature (40 DEG C～215 DEG C) of the Tg lower than resin bed, also show excellent processability in the methods such as temperature and pressure system.In addition, for resin bed, when temperature is higher, formability is better.In addition, due in order to keep shape (for not because strain returns to original state) after compacting, and carry out temperature and pressure system, thereby be also preferably from this viewpoint, even if for example, in the relatively high temperature (40 DEG C～215 DEG C) of the Tg lower than resin bed, also can maintain the ductility of copper foil composite.
It should be noted that, in the situation that copper foil composite contains bond layer and resin bed, adopt Tg(glass transition temperature) Tg of minimum layer.
[embodiment]
The manufacture > of < copper foil composite
The ingot casting being made up of tough pitch copper is carried out to hot calender, after removing oxide by surface cutting, repeat to cold pressing prolong, annealing and pickling, make it be thinned to the thickness t of table 1 2(mm), finally anneal and guarantee processability, carry out antirust processing by BTA, thereby obtain Copper Foil.For being become at width, organizes uniformly Copper Foil, and the contracting condition of the rolling homogeneous of make the to cold pressing tension force of time delay and the width of rolled material.In follow-up annealing, to become the mode of uniform Temperature Distribution at width, use multiple heaters to carry out temperature treatment, measure the temperature of copper and controlled.
And then, after the surface treatment shown in table 1 carry out respectively in the two sides of obtained Copper Foil, use the resin molding (resin bed) shown in table 1, with (Tg+50 DEG C of resin bed) above temperature by vacuum pressed (moulding pressure 200N/cm 2) laminated resin film, thereby make the copper foil composite of the layer structure shown in table 1.Embodiment 5 uses bonding agent and laminated copper foil and resin molding, thereby makes copper foil composite.
It should be noted that, in table 1, Cu represents Copper Foil, and PI represents polyimide film, and pet sheet shows polyethylene terephthalate film.In addition, the Tg of PI, PET is respectively 220 DEG C, 70 DEG C.
It should be noted that, form the Ni(alloy of the thickness shown in table 1 at the one side (not bonding with resin bed face) of Copper Foil) layer.The surface treatment shown in carry out table 1 at the opposing face (with the bonding plane of resin bed) of Copper Foil.Surface-treated condition is as described below.
Chromate processing: use chromic acid salt bath (K 2cr 2o 7: 0.5～5g/L), with current density 1～10A/dm 2carry out electrolytic treatments.The adhesion amount of the Cr oxide skin(coating) based on chromate processing is made as 35 μ g/dm 2.
Coating Ni+ chromate processing: use Ni plating bath (watt of Ni ion concentration: 1～30g/L is bathed), with 25～60 DEG C of plating solution temperature, current density 0.5～10A/dm 2plate after Ni, similarly carry out chromate processing with above-mentioned.The thickness of coating Ni is made as 0.010 μ m.
Roughening treatment: use treatment fluid (Cu:10～25g/L; H2SO4:20～100g/L), with 20～40 DEG C of temperature, current density 30～70A/dm 2, electrolysis time carries out electrolytic treatments for 1～5 second.,, use Ni-Co plating solution (Co ion concentration: 5～20g/L thereafter; Ni ion concentration: 5～20g/L; PH:1.0～4.0), with 25～60 DEG C of temperature, current density: 0.5～10A/dm 2plate Ni-Co.
It should be noted that, at the Ni(alloy of the non-bonding plane of Copper Foil) formation of layer is to carry out with the condition identical with above-mentioned coating Ni respectively.
In addition, the in the situation that of embodiment 24, form the Ni-Zn layer of thick 2.5 μ m at the non-bonding plane of Copper Foil.On the other hand, also form after Ni-Zn layer at the bonding plane of Copper Foil, similarly carry out chromate processing with above-mentioned.Ni-Zn layer is by using Ni-Zn plating to bathe (Ni ion concentration: 15～20g/L; Zn ion concentration: 10～20g/L), plating solution temperature 50 C, current density 4.0A/dm 2carry out plating and form.Analyze Ni-Zn layer, its result, alloy composition is Ni:Zn=75:25(wt%).
The in the situation that of embodiment 25, form the Ni-P layer of thick 2.5 μ m at the non-bonding plane of Copper Foil.On the other hand, also form after Ni-P layer at the bonding plane of Copper Foil, similarly carry out chromate processing with above-mentioned.Ni-P layer is by using Ni-P plating to bathe (Ni ion concentration: 15～20g/L; P concentration: 5g/L), 50～60 DEG C of plating solution temperature, current density 4A/dm 2carry out plating and form.Analyze Ni-P layer, its result, alloy composition is Ni:P=95:5(wt%).
The in the situation that of embodiment 26, form the Ni-Sn layer of thick 2.5 μ m at the non-bonding plane of Copper Foil.On the other hand, also form after Ni-Sn layer at the bonding plane of Copper Foil, similarly carry out chromate processing with above-mentioned.Ni-Sn layer is by using Ni-Sn plating to bathe (Ni ion concentration: 15～20g/L; Sn ion concentration: 10～15g/L), plating solution temperature 45 C, current density 4.0A/dm 2carry out plating and form.Analyze Ni-Sn layer, its result, alloy composition is Ni:Sn=80:20(wt%).
The in the situation that of embodiment 27, except the thickness of the Ni-Sn layer of the non-bonding plane of Copper Foil is changed to 0.3 μ m, operation forms each layer similarly to Example 26.Analyze Ni-Sn layer, its result, alloy composition is Ni:Sn=80:20(wt%).
The in the situation that of embodiment 28, form after Ni layer, Sn layer with the order of Ni layer, Sn layer at the non-bonding plane of Copper Foil, under blanket of nitrogen, apply the heat treatment of 180 DEG C, 7 hours.On the other hand, form after Ni layer at the bonding plane of Copper Foil, similarly carry out chromate processing with above-mentioned.Ni layer is by use sulfuric acid Ni bath (Ni ion concentration: 25g/L), with plating solution temperature 45 C, current density 4A/dm 2and form.Sn layer is by use phenolsulfonic acid bath (Sn ion concentration: 30g/L), with plating solution temperature 45 C, current density 8A/dm 2and form.Observe 2 electronic images of plating section of the non-bonding plane side of Copper Foil with SEM, its result is for being formed with 2 layers, analyzes the layer of top layer side, and its result is Ni:Sn=30:70(wt%), according to its result, be judged as Ni-Sn layer.The layer of analyzing base material side, its result is that Sn is below 5wt%, remainder is Ni, according to its result, is judged as Ni layer.The thickness of each layer be respectively 0.1 μ m(amount to thickness be 0.2 μ m).
The thickness of adhesion amount, Ni layer and the Ni alloy-layer of Cr oxide skin(coating) calculates as follows: the Copper Foil of the 100mm × 100mm that is formed with these layers is being mixed with to HNO 3(2 % by weight) and HCl(5 % by weight) solution in dissolve, and carry out the each metal concentration in quantitative this solution by ICP emission spectrophotometer (SII NanoTechnology Inc. manufacture, model SFC-3100), thereby calculate.Each sample is carried out to 5 times and measure, its mean value is made as to adhesion amount (thickness).
It should be noted that, the thickness of Ni layer and Ni alloy-layer is according to the quality of the each metal quantitatively obtaining by said method, uses known proportion to convert and obtains.
< tension test >
Made the tension test sheet of the short strip shape of multiple width 12.7mm by copper foil composite.About the tension test of Copper Foil and resin molding, the Copper Foil monomer before stacked and resin molding monomer are made to the short strip shape of 12.7mm.
Then,, by cupping machine, according to JIS-Z2241, carry out tension test in the direction parallel with the rolling direction of Copper Foil.Test temperature during by tension test is shown in table 1.
180 ° of disbonded test > of <
Carry out 180 ° of disbonded tests, measure 180 ° and peel off adhesive strength f 1.First, made the disbonded test sheet of the short strip shape of multiple width 12.7mm by copper foil composite.The copper-clad surface of test film is fixed on to SUS plate, peels off resin bed along 180 ° of directions.Be present in the embodiment on the two sides of resin bed about Copper Foil, removing after the Copper Foil of one side, the Copper Foil side of opposing face be fixed on to SUS plate, peel off resin bed along 180 ° of directions.Other conditions are according to JIS-C5016.
It should be noted that, be to peel off copper foil layer in the standard of JIS, and peeling off in an embodiment resin bed is in order to reduce by the thickness of Copper Foil, the impact that rigidity causes.
The evaluation > of < processability
Use the AEG-process device 10 shown in Fig. 2 to carry out the evaluation of processability.AEG-process device 10 possesses pedestal 4 and puncher 2, and pedestal 4 has the inclined-plane of circular cone shape, and the frustum of a cone from up to down front end attenuates, and the angle on the inclined-plane of the frustum of a cone becomes 60 ° with horizontal plane.In addition, at the downside of the frustum of a cone, be communicated with the circular hole of diameter 15mm and degree of depth 7mm.On the other hand, puncher 2 forms the hemispherical cylinder that front end is diameter 14mm, can insert to the circular hole of the frustum of a cone half bulb of puncher 2 front ends.
It should be noted that, the coupling part of the circular hole of the front end that the front end of the frustum of a cone attenuates and the downside of the frustum of a cone is with the circular arc of radius (r)=3mm.
Then, copper foil composite stamping-out is become to the discoideus test film 20 of diameter 30mm, and copper foil composite is loaded in the inclined-plane of the frustum of a cone of pedestal 4, puncher 2 is pressed down from test film 20 tops and insert towards the circular hole of pedestal 4.Thus, test film 20 is configured as taper cup-shaped.
It should be noted that, only exist resin bed at the one side of copper foil composite, resin bed is loaded upward in pedestal 4.In addition, exist resin bed on the two sides of copper foil composite, the resin bed bonding with M face loaded upward in pedestal 4.Be Cu on the two sides of copper foil composite, no matter which faces up all can.
Judge that by range estimation the Copper Foil in the test film 20 after shaping has crack-free, and carry out the evaluation of processability based on following benchmark.　
◎: Copper Foil does not break, Copper Foil is corrugationless also
Zero: Copper Foil does not break, but Copper Foil has a little fold
╳: Copper Foil breaks.
The corrosion proof evaluation of < >
Under pressure 98 ± 10KPa, to the face that is not laminated with resin bed in Copper Foil duplexer, after the salt solution that is 35 ± 2 DEG C by the temperature that is adjusted into sodium chloride concentration 5 ± 1wt%, pH=6.5～7.2 carries out spraying in 460 hours, visual observations outward appearance.In addition, the having or not this surface analysis Copper Foil composition by XPS.　
◎: unconfirmed have a variable color, and Copper Foil does not expose (not detecting Copper Foil composition from surface)
Zero: confirm the variable color just like white blur, Copper Foil does not expose (not detecting Copper Foil composition from surface)
╳: the green variable color that confirmation has the variable color of the black causing because of the oxidation of Copper Foil or causes because getting rusty, Copper Foil exposes (detecting Copper Foil composition from surface).
The evaluation > of the stability of < electric contact performance
By after each test film atmosphere heating 1000 hours, the copper-clad surface that is not laminated with resin bed is measured to contact resistance with 180 DEG C.The electric contact simulator CRS-1 that uses Shan Qijing machine company to manufacture, measures by four-terminal method.Probe: Au probe, contact load: 40g, sliding speed: 1mm/min, sliding distance: 1mm.　
Zero: contact resistance is lower than 10m Ω
╳: contact resistance is more than 10m Ω.
By obtained table 1, the table 2 of the results are shown in.It should be noted that, the test temperature of table 1 represents to carry out F, f 1, f 2, f 3, and the temperature of the evaluation of processability.
[table 1]
[table 2]
From table 1, table 2, the in the situation that of each embodiment, meet (f simultaneously 3× t 3)/(f 2× t 2)>=1 and 1≤33f 1/ (F × T), thus be the example of excellent in workability.In addition, the in the situation that of each embodiment, electric contact performance and corrosion resistance are also excellent.
It should be noted that, if the embodiment 15 of the Copper Foil duplexer that has used identical formation is compared with embodiment 19, known compared with embodiment 19, carry out tension test and measured (the f of the embodiment 15 of F etc. with room temperature (approximately 25 DEG C) 3× t 3)/(f 2× t 2) value larger, in embodiment 19, make resin bed tender (f because test temperature rises 3reduce).
On the other hand, in the case of Copper Foil not being carried out to surface treatment, the comparative example 1 of laminated resin film, adhesive strength reduces, 33f 1the value of/(F × T) is lower than 1, and processability is deteriorated.
Be decreased to 100N/cm at the moulding pressure when stacked 2the situation of comparative example 2,4 under, adhesive strength reduces, 33f 1the value of/(F × T) is lower than 1, and processability is deteriorated.
In the case of the comparative example 3 of the thickness of attenuate resin molding, resin film strength dies down compared with Copper Foil, (f 3× t 3)/(f 2× t 2) value lower than 1, processability is deteriorated.
In the case of not with the thickness of the plating Ni of the bonding face of resin bed the comparative example 5 lower than 0.001 μ m, electric contact performance and corrosion resistance are deteriorated.

Claims (6)

1. copper foil composite, it is the copper foil composite that Copper Foil and resin bed are laminated, and it is characterized in that:
The thickness of described Copper Foil is being made as to t 2(mm) stress of the described Copper Foil during, by elongation strain 4% is made as f 2(MPa), the thickness of described resin bed is made as to t 3(mm) stress of the described resin bed during, by elongation strain 4% is made as f 3(MPa), time, meet formula 1:(f 3× t 3)/(f 2× t 2)>=1;
And be made as f peeling off adhesive strength by 180 ° of described Copper Foil and described resin bed 1(N/mm), the intensity during by the elongation strain 30% of described copper foil composite is made as F(MPa), the thickness of described copper foil composite is made as to T(mm) time, meet formula 2:1≤33f 1/ (F × T);
The face that is not laminated with resin bed in described Copper Foil, is formed with the Ni layer and/or the Ni alloy-layer that amount to thickness 0.001～5.0 μ m.
2. copper foil composite as claimed in claim 1, is characterized in that, the total thickness of described Ni layer and/or Ni alloy-layer is 0.001～0.50 μ m.
3. copper foil composite as claimed in claim 1 or 2, is characterized in that, at the temperature of the glass transition temperature lower than described resin bed, described formula 1 and formula 2 are set up.
4. the copper foil composite as described in any one in claim 1～3, is characterized in that, the tension failure strain l of described copper foil composite and the ratio l/L of the tension failure strain L of described resin bed monomer are 0.7～1.
5. formed body, it processes the copper foil composite described in any one in claim 1～4.
6. the manufacture method of formed body, it is processed the copper foil composite described in any one in claim 1～4.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017189894A (en) * 2016-04-12 2017-10-19 宇部エクシモ株式会社 Metal laminate and metal molded body
CN114188543A (en) * 2021-11-15 2022-03-15 深圳市宝明科技股份有限公司 Composite conductive copper foil and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
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JP5497949B1 (en) * 2013-07-03 2014-05-21 Ｊｘ日鉱日石金属株式会社 Metal foil for electromagnetic wave shielding, electromagnetic wave shielding material and shielded cable
JP5887305B2 (en) 2013-07-04 2016-03-16 Ｊｘ金属株式会社 Metal foil for electromagnetic shielding, electromagnetic shielding material, and shielded cable
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011004664A1 (en) * 2009-07-07 2011-01-13 日鉱金属株式会社 Copper foil composite
JP2011210994A (en) * 2010-03-30 2011-10-20 Jx Nippon Mining & Metals Corp Copper foil for printed wiring board, and laminate using the same
CN102985252A (en) * 2010-07-15 2013-03-20 Jx日矿日石金属株式会社 Copper foil complex

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1195395C (en) * 2001-01-30 2005-03-30 日鉱金属股份有限公司 Copper alloy foil for integrated board
JP4683640B2 (en) 2006-01-31 2011-05-18 Ｊｘ日鉱日石金属株式会社 Copper foil for printed wiring board and printed wiring board using the same
JP5057932B2 (en) 2007-10-31 2012-10-24 Ｊｘ日鉱日石金属株式会社 Rolled copper foil and flexible printed wiring board
JP5185066B2 (en) 2008-10-23 2013-04-17 Ｊｘ日鉱日石金属株式会社 Copper foil excellent in flexibility, manufacturing method thereof, and flexible copper-clad laminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011004664A1 (en) * 2009-07-07 2011-01-13 日鉱金属株式会社 Copper foil composite
JP2011210994A (en) * 2010-03-30 2011-10-20 Jx Nippon Mining & Metals Corp Copper foil for printed wiring board, and laminate using the same
CN102985252A (en) * 2010-07-15 2013-03-20 Jx日矿日石金属株式会社 Copper foil complex

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017189894A (en) * 2016-04-12 2017-10-19 宇部エクシモ株式会社 Metal laminate and metal molded body
CN114188543A (en) * 2021-11-15 2022-03-15 深圳市宝明科技股份有限公司 Composite conductive copper foil and preparation method thereof

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