CN105074058A - Ultrathin copper foil with carrier, copper-clad laminate, and coreless substrate - Google Patents
Ultrathin copper foil with carrier, copper-clad laminate, and coreless substrate Download PDFInfo
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- CN105074058A CN105074058A CN201480008759.2A CN201480008759A CN105074058A CN 105074058 A CN105074058 A CN 105074058A CN 201480008759 A CN201480008759 A CN 201480008759A CN 105074058 A CN105074058 A CN 105074058A
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- copper foil
- thin copper
- extra thin
- metal
- peel ply
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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
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- 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
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- 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
Abstract
A carrier foil, an ultrathin copper foil, and an ultrathin copper foil with a carrier in which a separation layer is formed between the carrier foil and the ultrathin copper foil, wherein the invention is characterized in that the separation layer is formed under plating conditions such that the proportion in which a metal (B) is deposited is higher than the proportion in which a metal (A) is deposited, the separation layer comprising a first separation layer formed on the carrier foil side, and a second separation layer formed on the ultrathin copper foil side. The first separation layer comprises a metal (A) for retaining detachability, and a metal (B) for facilitating plating of the ultrathin copper foil. The ratio (x1) of elements of metal (A) and the ratio (y1) of elements of metal (B) satisfy the equation 70(%) < y1/(x1+y1)X100 below or equal to 79(%). The second separation layer comprises a metal (A) for retaining detachability, and a metal (B) for facilitating plating of the ultrathin copper foil. The ratio (x2) of elements of metal (A) and the ratio (y2) of elements of metal (B) satisfy the equation 80(%)& amp;lt; y2/(x2+y2)X100 below or equal to 88(%).
Description
Technical field
The band carrier extra thin copper foil that the present invention relates to a kind of applicable manufacture coreless substrate and the copper clad laminate be made up of the extra thin copper foil of this band carrier extra thin copper foil.
Background technology
Along with miniaturization, the slimming development of electronic machine, circuit substrate producer is considering to use the substrate of the realized slimming being called coreless substrate to manufacture multilayer laminate, and is tending towards the middle partial product laminar substrates used such as semiconductor packages to replace to coreless substrate.But coreless substrate supports the core of wiring layer owing to not existing, and therefore lacks rigidity, in the process forming wiring layer, may to bend, warpage, the problem such as to break.Therefore, people consider a kind of new-type manufacture method, using the foils of band carrier extra thin copper foil as supporter, at extra thin copper foil side lamination integrated circuit substrate, and the foils of last release band carrier extra thin copper foil, thus only take out coreless substrate.
Laminated substrate repeats lamination fine pitch wirings layer (lamination layer) up and down at supporter and core layer, forms high-density wiring.But described core layer adopts the traditional printing matrix technique be made up of glass epoxy resin etc., electrical specification deterioration can be caused.Especially, the larger inductance composition that the electroplating ventilating hole of through core layer has, becomes the major cause increasing semi-conductor chip power noise.For this reason, people are tending towards adopting the coreless substrate cancelling this core layer more.
Below, illustrate the concrete manufacturing process of band carrier extra thin copper foil as the coreless substrate of supporter.Coreless substrate manufactures via the operation of Fig. 1 (a) ~ (g) order.On the extra thin copper foil 2 of band carrier 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 the foils 5 forming fine pitch wirings band carrier extra thin copper foil, extra thin copper foil 6 is etched into the wiring pattern of regulation, forms fine pitch wirings 8.In fine pitch wirings 8, preimpregnation sheet material 4 of fitting once again, completes the first layer of coreless substrate.Repeat (b) ~ (d) operation, form coreless substrate 9 as on the band carrier extra thin copper foil of supporter.Then, peel off the foils 1 as supporter, finally utilize etching to wait and remove outermost extra thin copper foil 2, only take out the coreless substrate shown in (g), thus manufactured.
When manufacturing above-mentioned coreless substrate, be 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 foils 5, if the carrier stripping strength of band carrier extra thin copper foil 3 is not high, then the foils 1 being used as supporter may be stripped in the unexpected stage in coreless substrate manufacturing process.In addition, if carrier stripping strength is too high, then terminate in lamination, when peeling off coreless substrate, need more powerful, may cause coreless substrate that bending or warpage etc. occur, cause damage.Therefore, about the stripping strength from the foils 1 of release band carrier extra thin copper foil 3 on extra thin copper foil 2, although need suitable compactness in the manufacturing processes such as plating or etching, but finally will coreless substrate must being caused because of power operation impaired when peeling off, being therefore preferably 0.05kN/m ~ 0.15kN/m.
About the peel ply of band carrier extra thin copper foil, such as have the invention recorded in patent documentation 1 and 2, but the present inventor etc. think, they are not the inventions specially manufacturing coreless substrate, if these motions are directly used in manufacture coreless substrate, may meet accident problem.
Such as, patent documentation 1 (WO2010/27052 publication) principal concern is, consider the temperature of load when manufacturing multilayer laminate, for also easily peeling off foils and extra thin copper foil under 300 DEG C ~ 400 DEG C hot environments, stripping interface is divided into 2 layers, and specify the metal ratio of 2 layers of peel ply, thus easily peel off.
In addition, patent documentation 2 (Japanese Patent Publication 2007-186781 publication) define stripping strength lower and suppress bubble occur needed for, form 2 kinds of metal A of peel ply and the content of B.
But, contrary with the present invention, the exploitation object of these motions is, during making layer pressing plate, even if under load high temperature (300 DEG C ~ 400 DEG C) heating after pressurization, also carrier stripping strength is maintained lower, if the band carrier copper foil fabrication layer pressing plate, the especially coreless substrate that use this carrier stripping strength lower, the power of meeting owing to applying in lamination, the unexpected stage in lamination, there is stripping problem as between the foils of supporter and extra thin copper foil, there is risk.
Prior art document
Patent documentation
Patent documentation 1:WO2010/27052 publication
Patent documentation 2: Japanese Patent Publication 2007-186781 publication
Summary of the invention
(1) technical problem that will solve
As mentioned above, for preventing peeling off between the unexpected staging vector paper tinsel in veneer sheet lamination and Copper paper tinsel, the band carrier extra thin copper foil that a kind of carrier stripping strength is higher is needed.
Especially, after needing one to apply comparatively low temperature (being mainly 150 DEG C ~ 220 DEG C needed for glass epoxy substrate and the pressurization of bismaleimide-triazine resin substrate) heating when manufacture coreless substrate, become the band carrier extra thin copper foil of suitable high carrier stripping strength.
The object of the invention is, provides a kind of band carrier extra thin copper foil meeting this requirement, and uses the veneer sheet of this band carrier extra thin copper foil.
(2) technical scheme
Band carrier extra thin copper foil of the present invention, it has foils, extra thin copper foil and peel ply, and described peel ply is formed between described foils and described extra thin copper foil, and is made up of the metal A keeping separability and the metal B that easily carries out described extra thin copper foil plating, it is characterized in that
Described peel ply is made up of the first peel ply being formed at described foils side and the second peel ply of being formed at described extra thin copper foil side, in described first peel ply, suitably to improve for the purpose of carrier stripping strength, in order to reduce as the stripping metal A at interface or the ratio of its compound, the element of metal A is set to than y1 than x1 and the element of metal B
70％<{y1/(x1+y1)}×100≦79％，
Further, the element of metal A, also with same reason, is set to than y2 than x2 and the element of metal B by described second peel ply
80％<{y2/(x2+y2)}×100≦88％。
Band carrier extra thin copper foil of the present invention, the described foils preferably after carrying out 1 ~ 2 hour heat treated with the temperature of more than 150 DEG C, less than 220 DEG C and the stripping strength of described extra thin copper foil are for more than 0.05kN/m, below 0.15kN/m.
Band carrier extra thin copper foil of the present invention, preferred described metal A is from Mo, Ta, V, Mn, W, Cr, and comprise at least one metal or alloy selected in the alloy group of these elements, metal B is from Fe, Co, Ni, and comprises at least one metal or alloy selected in the alloy group of these elements.
Band carrier extra thin copper foil of the present invention, has barrier layer between preferred described foils and described peel ply.
Band carrier extra thin copper foil of the present invention, preferred described barrier layer by from Fe, Ni, Co, Cr, and comprises at least one metal or alloy selected in the alloy group of these elements and is formed.
Band carrier extra thin copper foil of the present invention, preferred described foils is copper or copper alloy.
Copper clad layers pressure substrate of the present invention, the band carrier extra thin copper foil of above-mentioned record is laminated on resin base material and is formed by it.
(3) beneficial effect
Band carrier extra thin copper foil of the present invention, can prevent the unexpected stage of multilayer laminate in lamination using this band carrier extra thin copper foil to manufacture, foils and Copper Foil are peeled off, and realize production process stabilization and productive rate raising.
Accompanying drawing explanation
Fig. 1 is using the manufacturing process mode chart of band carrier extra thin copper foil as the coreless substrate of supporter.
Fig. 2 is the mode chart representing band carrier extra thin copper foil embodiment of the present invention.
Fig. 3 is when representing manufacture band carrier extra thin copper foil of the present invention, the figure of current density condition during plating.
Embodiment
Fig. 2 is the embodiment of band carrier extra thin copper foil of the present invention, and this band carrier extra thin copper foil 10 is made up of foils 11, the barrier layer 12 being formed at this foils 11 surface, the peel ply 13 being formed at barrier layer 12 surface and the extra thin copper foil 16 that is formed at peel ply 13 surface.Peel ply 13 is made up of the first peel ply 14 being formed at described foils side and the second peel ply 15 of being formed at described extra thin copper foil side.When peeling off extra thin copper foil from foils, described first peel ply 14 stays foils side, and described second peel ply 15 stays described extra thin copper foil side.Even if peel ply only has above-mentioned first peel ply 14 one deck to form, also be expected to obtain the high carrier stripping strength same with the present invention, but the first peel ply 14 is in next operation, namely during copper strike plating, easily dissolve because of electroplating solution, therefore for preventing it, the second peel ply 15 must be formed, preventing the first peel ply 14 directly contact strike plating copper solutions.
As the foils 11 of band carrier extra thin copper foil 10, usually aluminium foil, alloy foil, stainless steel foil, titanium foil, titanium alloy foil, Copper Foil and copper alloy foil etc. can be used, but consider its ease-to-operate, be preferably electrolytic copper foil, electrolytic copper Alloy Foil, rolling Copper Foil or rolling copper alloy foil.
As the foils 11 of coreless substrate manufacturing process supporter, according to the comparatively thin copper foil of thickness less than 7 μm, then the physical strength of this foils 11 is weak, easily produces substrate fold or folding line, cannot play abundant effect as supporter when therefore manufacturing coreless substrate.In addition, if foils thickness is more than 200 μm, then the weight (coil monomer weight) of per unit coil increases, and causes production cost to increase, therefore undesirable.Therefore, as the thickness of foils, be preferably 7 μm ~ 200 μm persons.
Peel ply 13 is made up of the metal A keeping separability and the metal B that easily carries out extra thin copper foil plating.
As the metal A forming described peel ply, be select among interior alloy groups from Mo, Ta, V, Mn, W, Cr or containing these elements.Wherein, when considering process, liquid used is to the viewpoint of raw body security, especially preferably selects among interior alloy groups from Mo, Ta, V, Mn, W or containing these elements.In addition, metal B selects among interior alloy groups from Fe, Co, Ni or containing these elements.
As shown in Fig. 2 medelling, described peel ply 13 is made up of the first peel ply 14 being arranged at foils 11 side and the second peel ply 15 of being arranged at extra thin copper foil 16 side.
The present inventor etc. find after concentrating on studies, and form in the first peel ply 14 of peel ply 13, keep the metal A of separability to be set to the ratio of components (element ratio) of the metal B easily carrying out extra thin copper foil plating
70％<{y1/(x1+y1)}×100≦79％
Ratio is best.In addition, x1 is the element ratio of metal A, and y1 is the element ratio of metal B.
If aforementioned proportion is less than 70%, then carrier stripping strength is too low, the unexpected stage in veneer sheet lamination foils may occur and Copper Foil is peeled off; In addition, if aforementioned proportion is greater than 79%, then carrier stripping strength is too high, there will be the problem cannot peeling off extra thin copper foil.
The present inventor etc. find after concentrating on studies, and form in the second peel ply 15 of peel ply 13, keep the metal A of separability to be set to the ratio of components (element ratio) of the metal B easily carrying out extra thin copper foil plating
80％<{y2/(x2+y2)}×100≦88％
Ratio is best.In addition, x2 is the element ratio of metal A, and y2 is the element ratio of metal B.
If aforementioned proportion is less than 80%, then easily carry out the metal B of extra thin copper foil plating containing proportional very few, the extra thin copper foil that masking is formed there will be aperture or produces bubble, therefore undesirable; If more than 88%, then carrier stripping strength is too high, there will be the problem cannot peeling off extra thin copper foil from foils.
In addition, in metal A or metal B containing two or more with attribute metal time, using the element of same attribute metal than aggregate value as its element ratio.
the formation of barrier layer
For the separability of stable extra thin copper foil 16, also barrier layer can be formed on foils 11 surface.By so arranging barrier layer 12, the separability of peel ply 13 will be stablized and effectively.In the embodiment of the present invention, be that Ni is used as barrier layer, but Fe and Co also can obtain effect same.
the formation of peel ply
As an example of fabricated ribbon carrier extra thin copper foil 10, can first form the barrier layer 12 preventing foils Elements Diffusion on foils 11 surface, then form the first peel ply 14 and the second peel ply 15.
Above-mentioned each peel ply 14,15 is formed by metallide.
When changing the metal composition of each peel ply 14,15, realize by the concentration ratio (electrolyser construction) changing the metal A and metal B that are added into electrolyzer.
Or, not changing electrolyser construction, also changing metal composition by changing plating conditions.Such as, by changing current density, the metal composition of each peel ply can be changed.
the masking of extra thin copper foil
When forming extra thin copper foil 16, use copper sulfate pond, cupric pyrophosphate pond, thionamic acid pond and cupric cyanide pond etc., the second peel ply 15 is formed by metallide.In addition, according to the element of formation second peel ply 15, carry out in the metallide operation of extra thin copper foil masking, soak time in electroplating solution, current density, and when removing liquid after plating, washing time and the pH value of electroplating solution, all may cause negative impact to the second peel ply, therefore electrolytic plating pool structure and plating conditions etc., relation between necessary basis and the element forming the second peel ply, pays attention to and selects.
In addition, when the second peel ply carries out extra thin copper foil masking, be sometimes difficult to carry out uniformly-coating to peel ply, aperture can be occurred or produce bubble on the extra thin copper foil made.
So, when being difficult to carry out uniformly-coating, first cupric pyrophosphate pond etc. is used to carry out copper strike plating on the second peel ply 15 surface, thus reducing metal A oxide compound and formed compactness good densification basis electrolytic coating, and, on the second peel ply, implement uniformly-coating by implementing common copper facing, thus the little hole number that extra thin copper foil occurs can be reduced, prevent bubble from producing.
The copper facing thickness adhered to by described strike plating, is preferably 0.01 μm ~ 0.5 μm, although its condition is varied because pond kind is different, as current density, is preferably 0.1A/dm
2~ 20A/dm
2, as electroplating time, be preferably more than 0.1 second.If current density is 0.1A/dm
2below, be then difficult to evenly impose plating on peel ply, in addition, if 20A/dm
2above, then in the strike plating that electroplate liquid metal concentration is lower, plating can be there is and burn, even copper plate cannot be obtained, therefore undesirable.About electroplating time, if less than 0.1 second, then the time for obtaining abundant electrolytic coating is too short, therefore undesirable.As for the copper facing thickness be formed at by strike plating on peel ply, must be the thickness of nondestructively peeling layer separability, be 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 is after this temperature range, carrier stripping strength becomes best, and there is high carrier stripping strength, the intensity that this carrier stripping strength has, can fully bear in coreless substrate manufacturing process, the load in the etch processes that band carrier extra thin copper foil is formed circuit and the pressing treatment of carrying out lamination etc.
The peeling of band carrier extra thin copper foil of the present invention, its generation can be thought to form stripping interface owing to there is metal A oxide compound.About the precipitation mechanism of metal A oxide compound, clear and definite after contriver etc. concentrates on studies, if do not coexist with hydrogen as the metal oxide peeling off interface, then can not separate out.Hydrogen produces by polarizing (plating) on the current potential lower compared with hydrogen superpotential, if carry out on enough low current potential, then hydrogen will stablize generation, if but polarize near hydrogen superpotential, then the generation of hydrogen is by instability, carry out than on enough low current potential, hydrogen generation reduces.Current potential during plating, controls by changing current density.Increase after cathodic current, current potential toward lower one to conversion, in the Mo-Co alloy plating pond such as, used in the embodiment of the present invention, cathode current density 0.4A/dm
2time, current potential-1.12V (vs.Ag/AgCl/sat.KCl), negative electrode starts to produce unstable hydrogen.Afterwards, improve current density, reaching 1.0A/dm
2before (-1.22V (vs.Ag/AgCl/sat.KCl)), the obliquity of polarization curve is shown as fixed value-1.18V/decade, if but current density be increased to and be greater than 1.0A/dm
2, then the obliquity of polarization curve reduces, and than the region of polarization curve obliquity-1.18V/decade, hydrogen generating quantity increases sharply, and presents stable gas and produces.The carrier stripping strength specified in the present invention as shown in Figure 3, its realize be by by the first peel ply on polarization curve, in having the current potential (0.4A/dm of-1.18V/decade obliquity
2~ 1.0A/dm
2cathodic current) make in region.
In addition, shorten electroplating time merely, the amount of precipitation of metal A also can reduce, and therefore must adjust current density and time, controls the amount of precipitation of metal A oxide compound.Again investigate clearly rear to the plating conditions of patent documentation 1 and 2, it is under hydrogen produces the condition more stable compared with embodiment of the present invention, and electroplate for a long time, the metal A ratio therefore in peel ply is higher than application range of the present invention.On the other hand, in embodiments of the present invention, the amount of precipitation of metal A oxide compound is less, and the precipitation ratio of metal B uprises comparatively speaking, by the plating conditions that this is new, forms the weak peel ply of compactness, thus realize the object of high-peeling strength by being difficult to.
Below, the present invention is further described by embodiment.
Embodiment
[embodiment 1]
Be that the Copper Foil (thickness: 18 μm) of 1.1 μm, as foils, foils carries out Ni electroplating processes using monoplanar surface roughness Rz, form barrier layer.
Ni plating conditions:
Ni120g/L，
H
3BO
330g/L，
pH3.5，
Pond temperature 50 DEG C,
Current density 20A/dm
2,
Electroplating time 14.8s.
In the foils forming barrier layer, use Co-Mo electrolytic plating pool, with current density 0.4A/dm
2, electroplating time 6.0s forms the first peel ply.
Co-Mo plating conditions:
Mo8.0g/L，
Co4.0g/L，
Trisodium citrate 60g/L,
pH5.2，
Pond temperature 25 DEG C.
After forming the first peel ply, in Co-Mo liquid, soak 5.0s, after having soaked electroplate liquid, with current density 0.3A/dm
2, electroplating time 12.0s forms the second peel ply.
Then, on this peel ply, carry out copper strike plating with cupric pyrophosphate plating conditions, and utilize thin copper foil plating conditions to carry out copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
Cupric pyrophosphate plating conditions:
Cupric pyrophosphate 19g/L,
Potassium pyrophosphate 250g/L,
pH8.5，
Pond temperature 40 DEG C,
Current density 1.2A/dm
2,
Electroplating time 59.2s,
Extra thin copper foil foliation condition:
Cu70g/L，
H
2SO
450g/L，
Cl25ppm，
Current density 16.3A/dm
2,
Electroplating time 59.2s.
[embodiment 2 ~ 5]
Except by formed in embodiment 1 first peel ply plating conditions and except forming that the plating conditions of the second peel ply is as shown in table 1 and changing, other make band carrier extra thin copper foil all similarly to Example 1.
[embodiment 6]
In the foils identical with embodiment 1, form the barrier layer identical with embodiment 1.In the foils forming barrier layer, use Mo-Fe electrolytic plating pool, form the first peel ply.
Mo-Fe plating conditions:
Mo8.0g/L，
Fe3.7g/L，
Trisodium citrate 60g/L,
pH4.0，
Pond temperature 35 DEG C,
Current density 0.5A/dm
2,
Electroplating time 6.0s.
After forming the first peel ply, in Mo-Fe liquid, soak 5.0s.After having soaked electroplate liquid, with current density 0.3A/dm
2, electroplating time 12.0s forms the second peel ply.Then, similarly to Example 1, this peel ply is implemented copper strike plating and copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
[embodiment 7]
In the foils identical with embodiment 1, form the barrier layer identical with embodiment 1.In the foils forming barrier layer, use Mo-Ni electrolytic plating pool, form the first peel ply.
Mo-Ni plating conditions:
Mo24.0g/L，
Ni11.2g/L，
Trisodium citrate 60g/L,
pH10，
Pond temperature 25 DEG C,
Current density 0.8A/dm
2,
Electroplating time 6.0s.
After forming the first peel ply, in Mo-Ni liquid, soak 5.0s.After having soaked electroplate liquid, with current density 0.3A/dm
2, electroplating time 12.0s forms the second peel ply.Then, similarly to Example 1, this peel ply is implemented copper strike plating and copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
[embodiment 8]
In the foils identical with embodiment 1, form the barrier layer identical with embodiment 1.In the foils forming barrier layer, use W-Ni electrolytic plating pool, form the first peel ply.
W-Ni plating conditions:
W27.9g/L，
Ni11.2g/L，
Trisodium citrate 60g/L,
pH10，
Pond temperature 25 DEG C,
Current density 0.7A/dm
2,
Electroplating time 6.0s.
After forming the first peel ply, in W-Ni liquid, soak 5.0s.After having soaked electroplate liquid, with current density 0.3A/dm
2, electroplating time 12.0s forms the second peel ply.Then, similarly to Example 1, this peel ply is implemented copper strike plating and copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
Comparative example
[comparative example 1 and 2]
In the foils identical with embodiment 1, form the barrier layer identical with embodiment 1.In the foils forming barrier layer, use Mo-Co electrolytic plating pool, obviously be less than with hydrogen generating quantity or more than table 1 current density condition (than embodiment, the more polarization condition of noble potential and the polarization condition of more low potential) of embodiment 1, form the first peel ply.
After forming the first peel ply, in Mo-Co liquid, soak 5.0s.After having soaked electroplate liquid, with table 1 current density condition, form the second peel ply.Then, similarly to Example 1, this peel ply is implemented copper strike plating and copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
[comparative example 3 and 4]
In the foils identical with embodiment 1, form the barrier layer identical with embodiment 1.In the foils forming barrier layer, use Mo-Co electrolytic plating pool, with table 1 current density condition, form the first peel ply.
After forming the first peel ply, in Mo-Co liquid, soak 5.0s.After having soaked electroplate liquid, with table 1 current density condition (than embodiment, the more polarization condition of noble potential and the polarization condition of more low potential), form the second peel ply.Then, similarly to Example 1, this peel ply is implemented copper strike plating and copper facing, form the extra thin copper foil of 3 μm of thickness, as band carrier extra thin copper foil.
The band carrier extra thin copper foil made, behind 150 DEG C × 1 hour, 180 DEG C × 1 hour and heating in 220 DEG C × 2 hours, at pressure 30kgf/cm
2pressurize under condition, laminating extra thin copper foil and resin base material.Then, make the circuit that 10mm is wide, use the tensile testing machine (Japan's Baldwin manufactures, UTM-4-100) based on JISC6481-1996, foils is peeled off toward 90 degree of directions, measures carrier stripping strength.Measuring result is as shown in table 1.
Peel off from foils the test extra thin copper foil made, use fluorescent x-ray analyzer, measure remaining element (Mo, Co, Ni, W, Fe) adhesion amount in extra thin copper foil side and foils side.Measuring result is as shown in table 1.
[table 1]
Assessment result
[embodiment 1 ~ 8]
In embodiment 1 ~ 8, after peeling off foils and extra thin copper foil, in peel ply composition remaining on foils and extra thin copper foil, metal B proportion is respectively 70% ~ 79% and 80% ~ 89%.After within 150 DEG C × 1 hour, 180 DEG C × 1 hour and 220 DEG C × 2 hours, heating, carrier stripping strength is 0.050kN/m ~ 0.150kN/m, obtains the carrier stripping strength being applicable to manufacturing coreless substrate.
[comparative example 1]
In comparative example 1, after peeling off foils and extra thin copper foil, in peel ply composition remaining on foils and extra thin copper foil, metal B proportion is respectively 79.6% and 85.9%, and the metal B ratio of foils side exceeds the present invention and specifies.Therefore, after within 150 DEG C × 1 hour, 180 DEG C × 1 hour and 220 DEG C × 2 hours, heating, carrier stripping strength is higher than 0.150kN/m, although achieve high carrier stripping strength, but because carrier stripping strength is too high, when causing peeling off foils, the negative impacts such as bending, bending may be brought to coreless substrate, there is practicality problem.
[comparative example 2]
In comparative example 2, after peeling off foils and extra thin copper foil, in peel ply composition remaining on foils and extra thin copper foil, metal B proportion is less than 70%, lower than prescribed value of the present invention.Therefore, after within 150 DEG C × 1 hour, 180 DEG C × 1 hour and 220 DEG C × 2 hours, heating, carrier stripping strength, less than 0.050kN/m, cannot realize high carrier stripping strength.
[comparative example 3]
In comparative example 3, after peeling off foils and extra thin copper foil, in peel ply composition remaining on foils and extra thin copper foil, metal B proportion is more than 88%, and the metal B ratio of extra thin copper foil side specifies higher than the present invention.Therefore, after within 150 DEG C × 1 hour, 180 DEG C × 1 hour and 220 DEG C × 2 hours, heating, carrier stripping strength is higher than 0.150kN/m, although achieve high carrier stripping strength, but because carrier stripping strength is too high, when causing peeling off foils, the negative impacts such as bending, bending may be brought to coreless substrate, there is practicality problem.
[comparative example 4]
In comparative example 4, after peeling off foils and extra thin copper foil, in peel ply composition remaining on foils and extra thin copper foil, metal B proportion is less than 80%, and the metal B ratio of extra thin copper foil side specifies lower than the present invention.Therefore, after within 150 DEG C × 1 hour, 180 DEG C × 1 hour and 220 DEG C × 2 hours, heating, carrier stripping strength, less than 0.050kN/m, cannot realize high carrier stripping strength.
Use the band carrier extra thin copper foil manufactured in embodiment 1, find after manufacturing coreless substrate according to described coreless substrate manufacturing step, manufacturing process does not go wrong, and stripping process also can be peeled off smoothly.
Description of reference numerals
The 1 supporter 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 foils being with carrier extra thin copper foil
6 form the fine pitch wirings extra thin copper foil being with 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 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: foils, extra thin copper foil and peel ply, described peel ply is formed between described foils and described extra thin copper foil, and be made up of the metal A keeping separability and the metal B that easily carries out described extra thin copper foil plating, wherein, described peel ply is made up of the first peel ply being formed at described foils side and the second peel ply of being formed at described extra thin copper foil side, and the element of the metal A in described first peel ply than x1 and the element of metal B than y1 is
70％<{y1/(x1+y1)}×100≦79％，
Further, the element of the metal A in described second peel ply than x2 and the element of metal B than y2 is
80％<{y2/(x2+y2)}×100≦88％。
2. band carrier extra thin copper foil according to claim 1, it is characterized in that, stripping strength when the described foils after carrying out 1 ~ 2 hour heat treated with the temperature of more than 150 DEG C, less than 220 DEG C and described extra thin copper foil are at normal temperature is for more than 0.05kN/m, below 0.15kN/m.
3. band carrier extra thin copper foil according to claim 1 and 2, is characterized in that, described metal A is from Mo, Ta, V, Mn, W, Cr, and containing at least one metal or alloy selected in the alloy group of these elements,
Metal B is from Fe, Co, Ni, and comprises at least one metal or alloy selected in the alloy group of these elements.
4. band carrier extra thin copper foil according to any one of claim 1 to 3, is characterized in that having barrier layer between described foils and described peel ply.
5. band carrier extra thin copper foil according to claim 4, is characterized in that, described barrier layer by from Fe, Ni, Co, Cr, and comprises at least one metal or alloy selected in the alloy group of these elements and formed.
6. band carrier extra thin copper foil according to any one of claim 1 to 5, is characterized in that, described foils is copper or copper alloy.
7. a copper clad laminate, the band carrier extra thin copper foil according to any one of claim 1 to 6 is laminated on resin base material and is formed by it.
8. a coreless substrate, it uses the band carrier extra thin copper foil according to any one of claim 1 to 7 to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-035852 | 2013-02-26 | ||
| JP2013035852 | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105074058A true CN105074058A (en) | 2015-11-18 |
| CN105074058B CN105074058B (en) | 2016-11-23 |
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| CN201480008759.2A Active CN105074058B (en) | 2013-02-26 | 2014-02-25 | Band carrier extra thin copper foil, copper clad laminate and coreless substrate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5755371B2 (en) |
| KR (1) | KR101664993B1 (en) |
| CN (1) | CN105074058B (en) |
| TW (1) | TWI593830B (en) |
| WO (1) | WO2014132947A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382224A (en) * | 2017-01-16 | 2019-10-25 | 日进材料股份有限公司 | Extra thin copper foil with carrier foils |
| CN110662794A (en) * | 2017-03-29 | 2020-01-07 | 日立化成株式会社 | Prepreg for coreless substrate, method for manufacturing coreless substrate, and semiconductor package |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018009237A (en) * | 2016-07-15 | 2018-01-18 | Ｊｘ金属株式会社 | Copper foil with carrier, method for producing copper foil with carrier, laminate, method for producing laminate, method for manufacturing printed wiring board and method for manufacturing electronic equipment |
| 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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- 2014-02-25 CN CN201480008759.2A patent/CN105074058B/en active Active
- 2014-02-25 KR KR1020157019788A patent/KR101664993B1/en active IP Right Grant
- 2014-02-25 WO PCT/JP2014/054457 patent/WO2014132947A1/en active Application Filing
- 2014-02-26 TW TW103106418A patent/TWI593830B/en active
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Also Published As
| Publication number | Publication date |
|---|---|
| CN105074058B (en) | 2016-11-23 |
| JP5755371B2 (en) | 2015-07-29 |
| TW201437436A (en) | 2014-10-01 |
| KR101664993B1 (en) | 2016-10-11 |
| WO2014132947A1 (en) | 2014-09-04 |
| KR20150122632A (en) | 2015-11-02 |
| JPWO2014132947A1 (en) | 2017-02-02 |
| TWI593830B (en) | 2017-08-01 |
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