CN105074058B - Band carrier extra thin copper foil, copper clad laminate and coreless substrate - Google Patents

Band carrier extra thin copper foil, copper clad laminate and coreless substrate Download PDF

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Publication number
CN105074058B
CN105074058B CN201480008759.2A CN201480008759A CN105074058B CN 105074058 B CN105074058 B CN 105074058B CN 201480008759 A CN201480008759 A CN 201480008759A CN 105074058 B CN105074058 B CN 105074058B
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copper foil
thin copper
extra thin
metal
carrier
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CN105074058A (en
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藤田谅太
宇野岳夫
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
    • C25D1/22—Separating compounds
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing & Machinery (AREA)

Abstract

nullA kind of band carrier extra thin copper foil，It has carrier foils and extra thin copper foil，And between described carrier foils and described extra thin copper foil, form peel ply，It is characterized in that，Described peel ply is formed under metal B separates out the plating conditions that ratio separates out ratio higher than metal A，It is formed from the first peel ply of carrier foils side、And the second peel ply being formed at extra thin copper foil side is constituted，Described first peel ply is by the metal A keeping fissility and easily carries out the metal B of described extra thin copper foil plating and constitutes，The element of the metal A element than x1 and metal B is 70% ＜ { y1/ (x1+y1) } × 100≤79% than y1，And，Described second peel ply is by the metal A keeping fissility and easily carries out the metal B of described extra thin copper foil plating and constitutes，The element of the metal A element than x2 and metal B is 80% ＜ { y2/ (x2+y2) } × 100≤88% than y2.

Description

Band carrier extra thin copper foil, copper clad laminate and coreless substrate
Technical field
The present invention relates to the band carrier extra thin copper foil of a kind of applicable manufacture coreless substrate and by this The copper clad laminate that extra thin copper foil with carrier extra thin copper foil is constituted.
Background technology
Along with miniaturization, the slimming development of electronic machine, circuit substrate producer considers to make Manufacture multilayer laminate with the substrate of the realized slimming of referred to as coreless substrate, and tend to by The partial product laminar substrate used in semiconductor packages etc. replaces to coreless substrate.But, centreless base Plate supports the core of wiring layer owing to not existing, and therefore lacks rigidity, in the mistake forming wiring layer Cheng Zhong, it may occur that bending, warpage, the problem such as rupture.Therefore, people consider a kind of new Formula manufacture method, using the carrier foils of band carrier extra thin copper foil as supporter, in extra thin copper foil side Lamination integrated circuit substrate, is finally peeled away the carrier foils of band carrier extra thin copper foil, thus only takes out Coreless substrate.
Laminated substrate repeats to be laminated fine pitch wirings layer (lamination layer) in supporter i.e. core layer up and down, Form high-density wiring.But, described core layer uses the biography being made up of glass epoxy resin etc. System printed base plate technology, can cause electrical characteristic to deteriorate.Especially, the plating of through core layer is led to The bigger inductance composition that hole is had, becomes and increases the most former of semiconductor chip power noise Cause.To this end, people more tend to using the coreless substrate cancelling this core layer.
Hereinafter, illustrate to manufacture band carrier extra thin copper foil as the concrete of coreless substrate of supporter Operation.Coreless substrate manufactures via the operation of Fig. 1 (a)～(g) order.Carry at band On the extra thin copper foil 2 of body extra thin copper foil 3, laminating preimpregnation sheet material 4.On preimpregnation sheet material 4, Laminating forms fine pitch wirings band carrier extra thin copper foil 7.Peel off and form fine pitch wirings band carrier The carrier foils 5 of extra thin copper foil, is etched into the wiring pattern of regulation by extra thin copper foil 6, is formed thin Micro-wiring 8.In fine pitch wirings 8, the sheet material 4 of laminating preimpregnation once again, complete coreless substrate Ground floor.Repeat (b)～(d) operation, as on the band carrier extra thin copper foil of supporter Form coreless substrate 9.Then, peel off the carrier foils 1 as supporter, finally utilize etching Deng removing outermost extra thin copper foil 2, only take out the coreless substrate shown in (g), thus make Make.
When manufacturing above-mentioned coreless substrate, it is formed at the fine pitch wirings of internal layer in forming process, also Use band carrier extra thin copper foil.After Fig. 1 operation (b), when peeling off carrier foils 5, if Carrier peel strength with carrier extra thin copper foil 3 is the highest, then the carrier foils 1 being used as supporter can Can be stripped in the unexpected stage in coreless substrate manufacturing process.If additionally, carrier is peeled off strong Du Taigao, then terminate in lamination, when peeling off coreless substrate, needs relatively strength, may Cause coreless substrate that bending or warpage etc. occur, cause damage.Accordingly, with respect to from extra thin copper foil The peel strength of the carrier foils 1 of release band carrier extra thin copper foil 3 on 2, although in plating or erosion Ke Deng manufacturing process needs suitable compactness, but finally must will not be because of machinery when peeling off Operate and cause coreless substrate impaired, the most preferably 0.05kN/m～0.15kN/m.
About the peel ply of band carrier extra thin copper foil, such as, have described in patent documentation 1 and 2 Invention, but the present inventor etc. think, and they are not the most the inventions specially manufacturing coreless substrate, this If a little motions are directly used in manufacture coreless substrate, it may occur that unexpected problem.
Such as, patent documentation 1 (WO2010/27052 publication) principal concern is to examine Consider to manufacture multilayer laminate time load temperature, under 300 DEG C～400 DEG C of hot environments also It is easily peeled carrier foils and extra thin copper foil, stripping interface is divided into 2 layers, and specify 2 layers of peel ply Metal ratio, thus be easily peeled.
Additionally, patent documentation 2 (Japanese Patent Publication 2007-186781 publication) defines Peel strength relatively low and suppression bubble occur needed for, constitute peel ply 2 kinds of metal A and B Content.
But, contrary with the present invention, the exploitation purpose of these motions is, during making layer pressing plate, Even if under load high temperature (300 DEG C～400 DEG C) heats after pressurization, carrier is also maintained to peel off strong Spend relatively low, if using the relatively low band carrier copper foil of this carrier peel strength to manufacture laminate, outstanding Its coreless substrate, can be due to the power applied in lamination, the unexpected stage in lamination, As problem peeling-off between carrier foils and the extra thin copper foil of supporter, there is risk.
Prior art literature
Patent documentation
Patent documentation 1:WO2010/27052 publication
Patent documentation 2: Japanese Patent Publication 2007-186781 publication
Summary of the invention
(1) to solve the technical problem that
As it has been described above, for prevent the unexpected staging vector paper tinsel in laminate lamination and paper tinsel Between peeling-off, need the band carrier extra thin copper foil that a kind of carrier peel strength is higher.
Especially, one is needed to apply relatively low temperature (predominantly glass epoxide when manufacturing coreless substrate Needed for resin substrate and the pressurization of bismaleimide-triazine resin substrate 150 DEG C～220 DEG C) add After heat, become the band carrier extra thin copper foil of suitable high carrier peel strength.
Present invention aim at, it is provided that a kind of band carrier extra thin copper foil meeting this requirement, with And use the laminate of this band carrier extra thin copper foil.
(2) technical scheme
The band carrier extra thin copper foil of the present invention, it has carrier foils, extra thin copper foil and peel ply, Described peel ply is formed between described carrier foils and described extra thin copper foil, and by keeping fissility Metal A and easily carry out described extra thin copper foil plating metal B constitute, it is characterised in that
Described peel ply is formed from the first peel ply of described carrier foils side and is formed at institute The second peel ply stating extra thin copper foil side is constituted, in described first peel ply, to properly increase load For the purpose of body peel strength, in order to reduce as peeling off the metal A at interface or its compound Ratio, is set to the element of the metal A element than x1 with metal B than y1
70% < { y1/ (x1+y1) } × 100 79%,
Further, described second peel ply also with same reason, by the element of metal A than x2 with The element of metal B is set to than y2
80% < { y2/ (x2+y2) } × 100 88%.
The band carrier extra thin copper foil of the present invention, preferably with more than 150 DEG C, less than 220 DEG C Temperature carries out the stripping of the described carrier foils after 1～2 hour heat treated and described extra thin copper foil Intensity is more than 0.05kN/m, below 0.15kN/m.
The band carrier extra thin copper foil of the present invention, the most described metal A be from Mo, Ta, V, Mn, W, Cr, and comprise in the alloy group of these elements select at least one metal or Alloy, metal B is from Fe, Co, Ni, and comprises in the alloy group of these elements At least one metal or alloy selected.
The band carrier extra thin copper foil of the present invention, has between the most described carrier foils and described peel ply There is barrier layer.
The band carrier extra thin copper foil of the present invention, the most described barrier layer by from Fe, Ni, Co, Cr, and comprise at least one metal or alloy formation selected in the alloy group of these elements.
The band carrier extra thin copper foil of the present invention, the most described carrier foils is copper or copper alloy.
The copper clad layers pressure substrate of the present invention, the band carrier extra thin copper foil of above-mentioned record is laminated to by it Formed on resin base material.
(3) beneficial effect
The band carrier extra thin copper foil of the present invention, can prevent from using this band carrier extra thin copper foil to manufacture In the multilayer laminate unexpected stage in lamination, carrier foils is peeled off with Copper Foil, it is achieved produce Operation stabilisation and productivity improve.
Accompanying drawing explanation
Fig. 1 is as the manufacturing process mould of the coreless substrate of supporter using band carrier extra thin copper foil Formula figure.
Fig. 2 is the ideograph representing band carrier extra thin copper foil embodiment of the present invention.
When Fig. 3 is to represent manufacture band carrier extra thin copper foil of the present invention, current density condition during plating Figure.
Detailed description of the invention
Fig. 2 is the embodiment of band carrier extra thin copper foil of the present invention, this band carrier extra thin copper foil 10 barrier layers 12 by carrier foils 11, being formed at this carrier foils 11 surface, be formed at nonproliferation Dissipate the peel ply 13 on layer 12 surface and be formed at the extra thin copper foil 16 on peel ply 13 surface Constitute.Peel ply 13 is formed from the first peel ply 14 of described carrier foils side and is formed The second peel ply 15 in described extra thin copper foil side is constituted.When carrier foils peels off extra thin copper foil, Described first peel ply 14 stays carrier foils side, and described second peel ply 15 is stayed described ultra-thin Copper Foil side.Even if peel ply 14 1 layers of composition of the most above-mentioned first peel ply, also it is expected to obtain High carrier peel strength as the present invention, but the first peel ply 14 is in next operation, I.e. during copper strike plating, easily dissolve because of electroplating solution, therefore for preventing it, it is necessary to form the Two peel plies 15, prevent the first peel ply 14 from directly contacting strike plating copper solution.
As the carrier foils 11 of band carrier extra thin copper foil 10, aluminium foil, aluminum generally can be used to close Native gold, stainless steel foil, titanium foil, titanium alloy foil, Copper Foil and copper alloy foil etc., but consider To its ease-to-operate, preferably electrolytic copper foil, cathode copper Alloy Foil, rolling Copper Foil or Rolling copper alloy foil.
As the carrier foils 11 of coreless substrate manufacturing process supporter, according to thickness 7 μm with Under relatively thin copper foil, then the mechanical strength of this carrier foils 11 is weak, therefore manufacture coreless substrate time It is easily generated substrate fold or folding line, it is impossible to play abundant effect as supporter.If additionally, carrying Body paper tinsel thickness is more than 200 μm, then the weight (coil monomer weight) of per unit coil increases Add, cause production cost to increase, the most undesirable.Accordingly, as the thickness of carrier foils, excellent Elect 7 μm～200 μm persons as.
Peel ply 13 is by keeping the metal A of fissility and easily carrying out extra thin copper foil plating Metal B is constituted.
As constitute described peel ply metal A, be from Mo, Ta, V, Mn, W, Cr, Or select in interior alloy group containing these elements.Wherein, it is contemplated that medicinal liquid used during process Viewpoint to raw body safety, particularly preferably from Mo, Ta, V, Mn, W or containing this A little elements select in interior alloy group.Additionally, metal B be from Fe, Co, Ni or Select in interior alloy group containing these elements.
As shown in Fig. 2 medelling, described peel ply 13 is by being arranged at the first of carrier foils 11 side Peel ply 14 and be arranged at the second peel ply 15 of extra thin copper foil 16 side and constitute.
The present inventor etc. find after concentrating on studies, and constitute in the first peel ply 14 of peel ply 13, Keep the ratio of components (unit of the metal A and the metal B easily carrying out extra thin copper foil plating of fissility Element ratio) it is set to
70% < { y1/ (x1+y1) } × 100 79%
Ratio is optimal.It addition, x1 is the element ratio of metal A, y1 is the element ratio of metal B.
If aforementioned proportion is less than 70%, then carrier peel strength is too low, may be at laminate The unexpected stage in lamination occurs carrier foils to peel off with Copper Foil；If additionally, aforementioned proportion is big In 79%, then carrier peel strength is too high, it may appear that the problem that cannot peel off extra thin copper foil.
The present inventor etc. find after concentrating on studies, and constitute in the second peel ply 15 of peel ply 13, Keep the ratio of components (unit of the metal A and the metal B easily carrying out extra thin copper foil plating of fissility Element ratio) it is set to
80% < { y2/ (x2+y2) } × 100 88%
Ratio is optimal.It addition, x2 is the element ratio of metal A, y2 is the element ratio of metal B.
If aforementioned proportion is less than 80%, the most easily carry out the containing of metal B of extra thin copper foil plating Proportional very few, the extra thin copper foil that masking is formed there will be aperture or produces bubble, therefore pays no attention to Think；If more than 88%, then carrier peel strength is too high, it may appear that cannot peel off from carrier foils The problem of extra thin copper foil.
During it addition, metal A or metal B contains two or more with attribute metal, by same attribute The element of metal than aggregate value as its element ratio.
The formation of barrier layer
Fissility for stable extra thin copper foil 16, it is possible to form non-proliferation on carrier foils 11 surface Layer.By being arranged such barrier layer 12, the fissility of peel ply 13 is incited somebody to action stably effective. In the embodiment of the present invention, it is that Ni is used as barrier layer, but Fe and Co also can obtain equally Effect.
The formation of peel ply
As an example of manufacture band carrier extra thin copper foil 10, can be in carrier foils 11 surface first shape Become and prevent the barrier layer 12 of carrier foils Elements Diffusion, be subsequently formed the first peel ply 14 and the Two peel plies 15.
Above-mentioned each peel ply 14,15 can be formed by electrolysis plating.
When changing the metal composition of each peel ply 14,15, can add to electrolyzer by changing The concentration ratio (electrolyser construction) of metal A and metal B realize.
Or, do not change electrolyser construction, it is possible to change metal group by changing plating conditions Become.Such as, by changing electric current density, the metal composition of each peel ply can be changed.
The masking of extra thin copper foil
Formed extra thin copper foil 16 time, use copper sulfate pond, Copper pyrophosphate. pond, sulfamic acid pond, And copper cyanider pond etc., the second peel ply 15 is formed by electrolysis plating.It addition, root According to constituting the element of the second peel ply 15, carry out in the electrolysis electroplating work procedure of extra thin copper foil masking, Soak time in electroplating solution, electric current density, and plating after remove liquid time, washing Time and the pH value of electroplating solution, all the second peel ply may be adversely affected, therefore electricity Plating pool structure and plating conditions etc., it is necessary to according to constituting between the element of the second peel ply Relation, pays attention to and selects.
During additionally, carry out extra thin copper foil masking on the second peel ply, sometimes it is difficult to peel ply Carry out uniformly-coating, aperture can occur on the extra thin copper foil made or produce bubble.
So, it is difficult to when carrying out uniformly-coating, first Jiao is used on the second peel ply 15 surface Cupric phosphate pond etc. carries out copper strike plating, thus reducing metal A oxide form compactness Good fine and close basis electrodeposited coating, and, can be by implementing common copper facing on the second peel ply Implement uniformly-coating, thus the little hole number occurred on extra thin copper foil can be reduced, prevent bubble from producing Raw.
The copper facing thickness adhered to by described strike plating, preferably 0.01 μm～0.5 μm, though So its condition is varied because pond kind is different, but as electric current density, is preferably 0.1A/dm2～20A/dm2, as electroplating time, preferably more than 0.1 second.If electric current density For 0.1A/dm2Hereinafter, then it is difficult to uniformly impose plating on peel ply, if additionally, 20A/dm2Above, then in the strike plating that electroplate liquid metal concentration is relatively low, it may occur that plating is burnt Burnt, it is impossible to obtain uniform copper plate, the most undesirable.About electroplating time, if 0.1 second Hereinafter, then too short for obtaining the time of abundant electrodeposited coating, the most undesirable.As for by touching Hit the copper facing thickness that plating is formed on peel ply, it is necessary to be the thickness of nondestructively peeling layer fissility Degree, preferably 0.01～0.5 μm.After forming this strike plating layer, carry out the copper facing of desired thickness, Make extra thin copper foil.
When manufacturing coreless substrate, in suppression process, the temperature of load is 150 DEG C～220 DEG C.
The band carrier extra thin copper foil of present embodiment after this temperature range, carrier peel strength Become optimal, and there is high carrier peel strength, the intensity that this carrier peel strength has, can Fully bear in coreless substrate manufacturing process, band carrier extra thin copper foil is formed the etching of circuit Process and carry out the load in the compression process that is laminated etc..
The peeling of the band carrier extra thin copper foil of the present invention, it produces and is regarded as owing to existing Metal A oxide and formed stripping interface.About the precipitation mechanism of metal A oxide, warp Inventor etc. concentrate on studies after clearly, if as stripping interface metal-oxide not with hydrogen Coexist, then will not separate out.Hydrogen is by (the electricity that polarizes on the current potential that relatively hydrogen overvoltage is lower Plating) and produce, if carrying out on of a sufficiently low current potential, then hydrogen will stable produce, if but Polarize near hydrogen overvoltage, then the generation of hydrogen is by instability, than of a sufficiently low Carrying out on current potential, hydrogen generation amount reduces.Current potential during plating, can be close by changing electric current Degree is controlled.After increasing cathode current, current potential is changed toward relatively low direction, and the such as present invention is real Execute in the Mo-Co alloy plating pond used in example, cathode-current density 0.4A/dm2Time, electricity Position-1.12V (vs.Ag/AgCl/sat.KCl), negative electrode starts to produce unstable hydrogen.It After, improve electric current density, reach 1.0A/dm2(-1.22V(vs.Ag/AgCl/sat.KCl)) Before, the gradient of polarization curve is shown as fixed value-1.18V/decade, if but electric current is close Degree rises above 1.0A/dm2, then the gradient of polarization curve reduces, and inclines than polarization curve The region of gradient-1.18V/decade, hydrogen generating quantity increases sharply, and presents stable gas and produces Raw.In the present invention, the carrier peel strength of regulation is as it is shown on figure 3, its realization is by by first Peel ply is on polarization curve, in the current potential with-1.18V/decade gradient (0.4A/dm2～1.0A/dm2Cathode current) region makes.
Additionally, shorten merely electroplating time, the amount of precipitation of metal A also can reduce, therefore must Electric current density and time must be adjusted, control the amount of precipitation of metal A oxide.To patent documentation 1 And 2 plating conditions again investigate after clearly, it produces the relatively present invention at hydrogen and implements Under conditions of mode is more stable, electroplate for a long time, therefore the metal A ratio in peel ply Example is higher than the application range of the present invention.On the other hand, in embodiments of the present invention, metal A The amount of precipitation of oxide is less, and the precipitation ratio of metal B uprises comparatively speaking, new by this Plating conditions, it may be difficult to form the peel ply that compactness is weak, thus realize the mesh of high-peeling strength 's.
Hereinafter, the present invention is further described by embodiment.
Embodiment
[embodiment 1]
Using Copper Foil (thickness: 18 μm) that monoplanar surface roughness Rz is 1.1 μm as carrier Paper tinsel, carries out Ni electroplating processes in carrier foils, forms barrier layer.
Ni plating conditions:
Ni 120g/L,
H3BO330g/L,
PH 3.5,
Pond temperature 50 DEG C,
Electric current density 20A/dm2,
Electroplating time 14.8s.
In the carrier foils forming barrier layer, use Co-Mo electroplating pool, with electric current density 0.4A/dm2, electroplating time 6.0s form the first peel ply.
Co-Mo plating conditions:
Mo 8.0g/L,
Co 4.0g/L,
Trisodium citrate 60g/L,
PH 5.2,
Pond temperature 25 DEG C.
After forming the first peel ply, Co-Mo liquid soaks 5.0s, after having soaked electroplate liquid, With electric current density 0.3A/dm2, electroplating time 12.0s form the second peel ply.
Then, on this peel ply, copper strike plating is carried out with Copper pyrophosphate. plating conditions, and Utilize thin copper foil plating conditions to carry out copper facing, form the extra thin copper foil of 3 μ m thick, as band Carrier extra thin copper foil.
Copper pyrophosphate. plating conditions:
Copper pyrophosphate. 19g/L,
Potassium pyrophosphate 250g/L,
PH 8.5,
Pond temperature 40 DEG C,
Electric current density 1.2A/dm2,
Electroplating time 59.2s,
Extra thin copper foil foliation condition:
Cu 70g/L,
H2SO450g/L,
Cl 25ppm,
Electric current density 16.3A/dm2,
Electroplating time 59.2s.
[embodiment 2～5]
Except embodiment 1 will be formed the plating conditions of the first peel ply and form the second stripping Outside the plating conditions of absciss layer is changed as shown in table 1, other are made the most similarly to Example 1 Become band carrier extra thin copper foil.
[embodiment 6]
In carrier foils same as in Example 1, form barrier layer same as in Example 1. In the carrier foils forming barrier layer, use Mo-Fe electroplating pool, form the first peel ply.
Mo-Fe plating conditions:
Mo 8.0g/L,
Fe 3.7g/L,
Trisodium citrate 60g/L,
PH 4.0,
Pond temperature 35 DEG C,
Electric current density 0.5A/dm2,
Electroplating time 6.0s.
After forming the first peel ply, Mo-Fe liquid soaks 5.0s.After having soaked electroplate liquid, With electric current density 0.3A/dm2, electroplating time 12.0s form the second peel ply.Then, with reality Execute example 1 same, this peel ply is implemented copper strike plating and copper facing, forms 3 μ m thick Extra thin copper foil, as band carrier extra thin copper foil.
[embodiment 7]
In carrier foils same as in Example 1, form barrier layer same as in Example 1. In the carrier foils forming barrier layer, use Mo-Ni electroplating pool, form the first peel ply.
Mo-Ni plating conditions:
Mo 24.0g/L,
Ni 11.2g/L,
Trisodium citrate 60g/L,
PH 10,
Pond temperature 25 DEG C,
Electric current density 0.8A/dm2,
Electroplating time 6.0s.
After forming the first peel ply, Mo-Ni liquid soaks 5.0s.After having soaked electroplate liquid, With electric current density 0.3A/dm2, electroplating time 12.0s form the second peel ply.Then, with reality Execute example 1 same, this peel ply is implemented copper strike plating and copper facing, forms 3 μ m thick Extra thin copper foil, as band carrier extra thin copper foil.
[embodiment 8]
In carrier foils same as in Example 1, form barrier layer same as in Example 1. In the carrier foils forming barrier layer, use W-Ni electroplating pool, form the first peel ply.
W-Ni plating conditions:
W 27.9g/L,
Ni 11.2g/L,
Trisodium citrate 60g/L,
PH 10,
Pond temperature 25 DEG C,
Electric current density 0.7A/dm2,
Electroplating time 6.0s.
After forming the first peel ply, W-Ni liquid soaks 5.0s.After having soaked electroplate liquid, With electric current density 0.3A/dm2, electroplating time 12.0s form the second peel ply.Then, with reality Execute example 1 same, this peel ply is implemented copper strike plating and copper facing, forms 3 μ m thick Extra thin copper foil, as band carrier extra thin copper foil.
Comparative example
[comparative example 1 and 2]
In carrier foils same as in Example 1, form barrier layer same as in Example 1. In the carrier foils forming barrier layer, use Mo-Co electroplating pool, bright with hydrogen generating quantity Aobvious table 1 current density condition fewer of more than embodiment 1 (than embodiment, more high potential Polarization condition and the polarization condition of more electronegative potential), form the first peel ply.
After forming the first peel ply, Mo-Co liquid soaks 5.0s.After having soaked electroplate liquid, With table 1 current density condition, form the second peel ply.Then, similarly to Example 1, exist Implement copper strike plating and copper facing on this peel ply, form the extra thin copper foil of 3 μ m thick, make For band carrier extra thin copper foil.
[comparative example 3 and 4]
In carrier foils same as in Example 1, form barrier layer same as in Example 1. In the carrier foils forming barrier layer, use Mo-Co electroplating pool, with table 1 electric current density Condition, forms the first peel ply.
After forming the first peel ply, Mo-Co liquid soaks 5.0s.After having soaked electroplate liquid, With table 1 current density condition (polarization condition and the more electronegative potential than embodiment, more high potential Polarization condition), form the second peel ply.Then, similarly to Example 1, in this stripping Implement copper strike plating and copper facing on layer, form the extra thin copper foil of 3 μ m thick, carry as band Body extra thin copper foil.
The band carrier extra thin copper foil made, through 150 DEG C × 1 hour, 180 DEG C × 1 hour, with And after heating in 220 DEG C × 2 hours, at pressure 30kgf/cm2Under the conditions of pressurize, ultra-thin copper of fitting Paper tinsel and resin base material.Then, make the wide circuit of 10mm, use based on JIS C 6481-1996 Cupping machine (Japan Baldwin manufacture, UTM-4-100), by carrier foils toward 90 degree just To stripping, measure carrier peel strength.Measurement result is as shown in table 1.
From carrier foils, peel off the test extra thin copper foil made, use x-ray fluorescence analysis dress Put, measure extra thin copper foil side and carrier foils side remaining element (Mo, Co, Ni, W, Fe) adhesion amount.Measurement result is as shown in table 1.
[table 1]
Assessment result
[embodiment 1～8]
In embodiment 1～8, after peeling off carrier foils and extra thin copper foil, in carrier foils and extra thin copper foil In the peel ply composition of remaining, metal B proportion is respectively 70%～79% and 80%～89%. After 150 DEG C × 1 hour, 180 DEG C × 1 hour and heating in 220 DEG C × 2 hours, carrier is shelled It is 0.050kN/m～0.150kN/m from intensity, it is thus achieved that the carrier being suitable for manufacturing coreless substrate is peeled off Intensity.
[comparative example 1]
In comparative example 1, after peeling off carrier foils and extra thin copper foil, residual in carrier foils and extra thin copper foil In the peel ply composition deposited, metal B proportion is respectively 79.6% and 85.9%, carrier foils The metal B ratio of side is beyond present invention provide that.Therefore, 150 DEG C × 1 hour, 180 DEG C × 1 Hour and 220 DEG C × 2 hours heating after, carrier peel strength be higher than 0.150kN/m, Although achieving high carrier peel strength, but because carrier peel strength is too high, cause peeling off load During body paper tinsel, coreless substrate may be brought the negative effects such as bending, bending, there is practicality Problem.
[comparative example 2]
In comparative example 2, after peeling off carrier foils and extra thin copper foil, residual in carrier foils and extra thin copper foil In the peel ply composition deposited, metal B proportion is less than 70%, less than present invention provide that Value.Therefore, 150 DEG C × 1 hour, 180 DEG C × 1 hour and heating in 220 DEG C × 2 hours After, carrier peel strength is less than 0.050kN/m, it is impossible to realize high carrier peel strength.
[comparative example 3]
In comparative example 3, after peeling off carrier foils and extra thin copper foil, residual in carrier foils and extra thin copper foil In the peel ply composition deposited, metal B proportion is more than 88%, the gold of extra thin copper foil side Belong to B ratio higher than present invention provide that.Therefore, 150 DEG C × 1 hour, 180 DEG C × 1 hour, And after heating in 220 DEG C × 2 hours, carrier peel strength is higher than 0.150kN/m, although real Show high carrier peel strength, but because carrier peel strength is too high, when causing peeling off carrier foils, Coreless substrate may be brought the negative effects such as bending, bending, there is practicality problem.
[comparative example 4]
In comparative example 4, after peeling off carrier foils and extra thin copper foil, residual in carrier foils and extra thin copper foil In the peel ply composition deposited, metal B proportion is less than 80%, the gold of extra thin copper foil side Belong to B ratio less than present invention provide that.Therefore, 150 DEG C × 1 hour, 180 DEG C × 1 hour, And after heating in 220 DEG C × 2 hours, carrier peel strength is less than 0.050kN/m, it is impossible to real Existing high carrier peel strength.
Use the band carrier extra thin copper foil manufactured in embodiment 1, manufacture according to described coreless substrate Step finds after manufacturing coreless substrate, and manufacturing process does not goes wrong, and stripping process also can be smooth Peel off.
Description of reference numerals
The 1 supporter carrier foils of band carrier extra thin copper foil
The 2 supporters extra thin copper foil of band carrier extra thin copper foil
3 supporters band carrier extra thin copper foil
4 preimpregnation sheet materials
5 form the fine pitch wirings carrier foils of band carrier extra thin copper foil
6 form the fine pitch wirings extra thin copper foil of band carrier extra thin copper foil
7 form fine pitch wirings band carrier extra thin copper foil
8 fine pitch wirings
9 coreless substrates
10 band carrier extra thin copper foils
11 carrier foils
12 barrier layers
13 peel plies
14 first peel plies
15 second peel plies
16 extra thin copper foils

Claims (8)

1. a band carrier extra thin copper foil, it has: carrier foils, extra thin copper foil and peel ply, Described peel ply is formed between described carrier foils and described extra thin copper foil, and by from Mo or W A kind of metal A of middle selection and a kind of metal B selected from Fe, Co, Ni is constituted,
Wherein, described peel ply is by two-layer, i.e. be formed at the first stripping of described carrier foils side Layer and be formed at described extra thin copper foil side second peel ply constitute,
The element of the metal A in the described first peel ply element than x1 and metal B compares y1 For
70% < { y1/ (x1+y1) } × 100 79%,
Further, the element of the metal A in the described second peel ply element than x2 Yu metal B Than y2 it is
80% < { y2/ (x2+y2) } × 100 88%.
Band carrier extra thin copper foil the most according to claim 1, it is characterised in that with More than 150 DEG C, the temperature of less than 220 DEG C carry out the described carrier foils after 1～2 hour heat treated With the described extra thin copper foil peel strength when room temperature be more than 0.05kN/m, 0.15kN/m with Under.
Band carrier extra thin copper foil the most according to claim 1 and 2, it is characterised in that Between described carrier foils and described peel ply, there is barrier layer.
Band carrier extra thin copper foil the most according to claim 3, it is characterised in that described Barrier layer is by from Fe, Ni, Co, Cr, and comprises in the alloy group of these elements and select At least one metal or alloy formed.
5. according to the band carrier extra thin copper foil according to any one of claim 1,2,4, its Being characterised by, described carrier foils is copper or copper alloy.
Band carrier extra thin copper foil the most according to claim 3, it is characterised in that described Carrier foils is copper or copper alloy.
7. a copper clad laminate, the band according to any one of claim 1 to 6 is carried by it Body extra thin copper foil is laminated on resin base material be formed.
8. a coreless substrate, it uses the band according to any one of claim 1 to 6 to carry Body extra thin copper foil is made.
CN201480008759.2A 2013-02-26 2014-02-25 Band carrier extra thin copper foil, copper clad laminate and coreless substrate Active CN105074058B (en)

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JP2013-035852 2013-02-26
PCT/JP2014/054457 WO2014132947A1 (en) 2013-02-26 2014-02-25 Ultrathin copper foil with carrier, copper-clad laminate, and coreless substrate

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KR101944783B1 (en) 2017-01-16 2019-04-18 일진머티리얼즈 주식회사 Copper foil attached to the carrier foil
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KR102137068B1 (en) * 2019-11-27 2020-07-23 와이엠티 주식회사 Carrier foil with metal foil, manufacturing method of the same, and laminate comprising the same

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KR101664993B1 (en) 2016-10-11
CN105074058A (en) 2015-11-18
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WO2014132947A1 (en) 2014-09-04
TWI593830B (en) 2017-08-01

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