CN104717831B - Surface treatment copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board - Google Patents

Surface treatment copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board Download PDF

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Publication number
CN104717831B
CN104717831B CN201410707733.9A CN201410707733A CN104717831B CN 104717831 B CN104717831 B CN 104717831B CN 201410707733 A CN201410707733 A CN 201410707733A CN 104717831 B CN104717831 B CN 104717831B
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copper foil
carrier
layer
copper
thin layers
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CN104717831A (en
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森山晃正
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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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to the manufacture method of surface treatment copper foil, laminate, printed wiring board, e-machine, Copper foil with carrier and printed wiring board, there is provided even if a kind of be used for high-frequency circuit board, also suppresses the surface treatment copper foil of transmission loss well.The surface treatment copper foil of the present invention is that total adhesion amount of Co, Ni, Fe in surface treatment copper foil of at least one surface formed with surface-treated layer, surface-treated layer are 1000 μ g/dm2Below, surface-treated layer has Zn metal levels or the alloy treatment layer containing Zn, it is 1.0~1.9 relative to the ratio of bivariate table area that layer surface, which is surface-treated, using the three-dimensional table area measured by laser microscope, and the surface roughness Rz JIS at least one surface are less than 2.2 μm.

Description

Surface treatment copper foil, laminate, printed wiring board, e-machine, Copper foil with carrier, And the manufacture method of printed wiring board
Technical field
The present invention relates to a kind of surface treatment copper foil, laminate, printed wiring board, e-machine, Copper foil with carrier and print The manufacture method of brush wiring plate, more particularly to a kind of surface treatment copper foil of suitable high-frequency circuit board purposes, laminate, print Brush wiring plate, e-machine, the manufacture method of Copper foil with carrier and printed wiring board.
Background technology
On printed wiring board, made great progress since this half a century, nowadays have been used for essentially all electricity Handset device.As the miniaturization to e-machine in recent years, the requirement of high performance increase, the high-density packages of part are carried Or the high frequency progress of signal, require that excellent high frequency is corresponding for printed wiring board.
For high frequency substrate, in order to ensure the quality of output signal, and require to reduce transmission loss.Transmission loss The main conductor losses for being the dielectric medium loss of resin (substrate-side) including reason, being conductor (copper foil side) with reason.Close It is lost in dielectric medium, the dielectric constant and dielectric loss tangent of resin become smaller, and dielectric medium loss is more reduced.Believe in high frequency Number when, be the main reason for conductor losses：Frequency becomes higher, because electric current is only in the skin effect that becomes of the surface flow of conductor Should, the sectional area that electric current is flowed through more is reduced, and resistance more uprises.
As the technology for the transmission loss for reducing high frequency copper foil, such as announcement has a kind of high-frequency electrical in patent document 1 Road metal foil, it is coated to silver or silver alloy category in the one or two sides of metal foil surface, on the silver or silver alloy coating The coating for setting thickness to be less than beyond the silver or silver alloy of the silver or silver alloy coating.Moreover, following situation is recorded, Can be according to the high-frequency circuit metal foil, and a kind of metal foil is provided, even if it is in the superelevation as used in satellite communication In frequency domain, the loss as caused by Kelvin effect is also reduced.
In addition, being disclosed in patent document 2 has a kind of high-frequency circuit roughening treatment rolled copper foil, it is characterised in that：Its Tellite material, and after the recrystallization annealing of rolled copper foil calendering face by calculated by X ray diffraction (200) integrated intensity (I (200)) in face is strong relative to the integration by (200) face calculated by X ray diffraction of fine powder copper Spend (I0(200)), it is I (200)/I0(200) ＞ 40, and the calendering face is carried out thick after the roughening treatment using electrolysis plating The arithmetic average roughness (following, to be set to Ra) for changing process face is 0.02 μm~0.2 μm, and 10 mean roughness (below, are set to Rz) it is 0.1 μm~1.5 μm.Moreover, record following situation, you can according to high-frequency circuit roughening treatment rolled copper foil, And provide the printed circuit board (PCB) that can be used at high frequencies over ighz.
And then announcement has a kind of electrolytic copper foil in patent document 3, it is characterised in that：The part on the surface of copper foil is The male and fomale(M＆F) that the surface roughness being made up of block-like protrusions is 2~4 μm.Moreover, record following situation, you can according to the electricity Copper foil is solved, and provides frequency transfer characteristic excellent electrolytic copper foil.
[prior art literature]
[patent document]
No. 4161304 publications of [patent document 1] Japanese Patent No.
No. 4704025 publications of [patent document 2] Japanese Patent No.
[patent document 3] Japanese Patent Laid-Open 2004-244656 publications
The content of the invention
[problems to be solved by the invention]
It is the conductor losses of conductor (copper foil side) on reason, its reason is to make electricity because of Kelvin effect as described Resistive is big, on the resistance, the not only influence of the resistance of copper foil in itself, also have copper foil surface by order to ensure with resin The adherence of substrate and the roughening treatment carried out and the influence of the resistance of surface-treated layer formed, specifically, copper foil surface Roughness the main reason for being conductor losses, it is known that roughness is smaller, and transmission loss is more reduced.
In addition, in the case where carrying out roughening treatment as the surface treatment of copper foil, usually using Cu-Ni alloy treatments Or Cu-Co-Ni alloy treatments, in the case where carrying out resistance to heat treatment and antirust treatment as the surface treatment of copper foil, generally Use Ni-Zn alloy treatments or Co-Ni alloy treatments.
However, the Co and Ni and then Fe that are generally used in the roughening treatment, resistance to heat treatment and antirust treatment are normal Ferromagnetic metal is shown under temperature, as composition and in the case of being contained in surface-treated layer, following problem can be produced： Because of the influence of magnetic, CURRENT DISTRIBUTION and Distribution of Magnetic Field in conductor are affected, and cause the transmission characteristic of copper foil to be deteriorated.
Even if it is an object of the invention to provide one kind to be used for high-frequency circuit board, also suppress the table of transmission loss well Face handles the manufacture method of copper foil, laminate, printed wiring board, e-machine, Copper foil with carrier and printed wiring board.
[technological means for solving problem]
The inventors have found that in order to suppress influence of the ferromagnetism metal to transmission characteristic, can be by the surface by copper foil at The total adhesion amount for managing Co, Ni, Fe in layer is controlled below specified quantitative, and is contained and do not shown ferromagnetic Zn at normal temperatures As replacement composition, and further reduce high-frequency transmission loss.And then find, high frequency copper foil managed except conventional Surface roughness Rz is significantly affected outside transmission loss, more accurately represents the three-dimensional surface with the contact area of resin (dielectric medium) Product also significantly affects transmission loss relative to the ratio of bivariate table area.
The present invention completed based on the opinion is a kind of surface treatment copper foil, at least one in an aspect Formed with surface-treated layer, total adhesion amount of Co, Ni, Fe in the surface-treated layer are 1000 μ g/dm on surface2Hereinafter, The surface-treated layer has Zn metal levels or the alloy treatment layer containing Zn, and the surface treatment layer surface utilizes laser capture microdissection Three-dimensional table area measured by mirror is 1.0~1.9 relative to the ratio of bivariate table area, the surface roughness Rz at least one surface JIS is less than 2.2 μm.
In one embodiment, Co, Ni, Fe's in the surface-treated layer is total for the surface treatment copper foil of the present invention Adhesion amount is 500 μ g/dm2Below.
The present invention surface treatment copper foil in another embodiment, the conjunction of Co, Ni, Fe in the surface-treated layer Meter adhesion amount is 300 μ g/dm2Below.
The surface treatment copper foil of the present invention is in further embodiment, the conjunction of Co, Ni, Fe in the surface-treated layer Meter adhesion amount is 0 μ g/dm2。
For the surface treatment copper foil of the present invention in further embodiment, the surface roughness Rz JIS on two surfaces are 2.2 μ Below m.
For the surface treatment copper foil of the present invention in further embodiment, the surface-treated layer includes roughening treatment layer.
In further embodiment, the adhesion amount of the Cu in the roughening treatment layer is the surface treatment copper foil of the present invention 0.10g/dm2Below.
The surface treatment copper foil of the present invention is in further embodiment, in the surface-treated layer, in the roughening The Zn metal levels or the alloy treatment layer containing Zn are provided with process layer.
For the surface treatment copper foil of the present invention in further embodiment, the alloy treatment layer containing Zn is Cu-Zn Alloy-layer.
In further embodiment, the adhesion amount of the Zn in the surface-treated layer is the surface treatment copper foil of the present invention 5mg/dm2Below.
The surface treatment copper foil of the present invention is in further embodiment, in the surface-treated layer, in Zn gold Chromating layer is provided with category layer or alloy treatment layer containing Zn.
The surface treatment copper foil of the present invention is provided with silane in further embodiment on the chromating layer Coupling processing layer.
The surface treatment copper foil of the present invention in further embodiment, Cu, Zn, Co, Ni in the surface-treated layer, Fe total adhesion amount is 0.10g/dm2Below.
The surface treatment copper foil of the present invention is to be used for soft printing wiring plate in further embodiment.
The surface treatment copper foil of the present invention is the high-frequency circuit board for more than 5GHz in further embodiment.
The present invention is a kind of laminate in another aspect, is by the surface treatment copper foil and resin substrate of the present invention It is laminated and is manufactured.
The present invention is a kind of printed wiring board in another aspect, and it is to be used as material using the laminate of the present invention.
The present invention is a kind of e-machine in another aspect, and it uses the printed wiring board for having the present invention.
The present invention is a kind of Copper foil with carrier in another aspect, sequentially has centre in the one or both sides of carrier Layer, very thin layers of copper, the very thin layers of copper are surface treatment copper foil of the invention.
The Copper foil with carrier of the present invention in one embodiment, sequentially has the centre in the one side of the carrier Layer, the very thin layers of copper, have roughening treatment layer in the another side of the carrier.
The present invention is a kind of laminate in another aspect, and it is by the Copper foil with carrier and resin substrate of the present invention It is laminated and is manufactured.
The present invention is a kind of manufacture method of printed wiring board, it comprises the following steps in another aspect：
The step of preparing the Copper foil with carrier and insulated substrate of the present invention；
The step of Copper foil with carrier and insulated substrate are laminated；And
After the Copper foil with carrier and insulated substrate are laminated, by what the carrier of the Copper foil with carrier was peeled off Step and form metal-coated laminated board, thereafter, by semi-additive process, subtractive process, part addition process or improve semi-additive process in Any method and the step of form circuit.
The present invention is a kind of manufacture method of printed wiring board, it comprises the following steps in another aspect：
In the very thin layers of copper side surface of Copper foil with carrier of the present invention or the step of the carrier side circuit forming surface Suddenly；
In a manner of burying the circuit, in the very thin layers of copper side surface of the Copper foil with carrier or the carrier side Surface forms the step of resin bed；
On the resin bed formed circuit the step of；
After forming circuit on the resin bed, the step of the carrier or the very thin layers of copper are peeled off；And
After the carrier or the very thin layers of copper are peeled off, the very thin layers of copper or the carrier are removed, thus make shape Into the step of being exposed in the very thin layers of copper side surface or the carrier side surface by the circuit that the resin bed is buried.
[The effect of invention]
According to the present invention, it is possible to provide even if being used for high-frequency circuit board, also suppress the surface treatment of transmission loss well Copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board.
Brief description of the drawings
Fig. 1 is Co, Ni, Fe for representing embodiment and comparative example total adhesion amount, the relation with surface roughness Rz Chart.
Fig. 2 be Co, Ni, Fe for representing embodiment and comparative example total adhesion amount, with three-dimensional table area relative to two dimension The chart of the relation of the ratio of surface area.
Fig. 3 is Co, Ni, Fe, Cu, Zn for representing embodiment and comparative example total adhesion amount, the relation with transmission loss Chart.
Embodiment
(copper foil base material)
Form available for the copper foil base material of the present invention is not particularly limited, can be with rolled copper foil or electrolysis for typical case The form of copper foil and use.In general, electrolytic copper foil is copper is separated out turn to titanium or stainless steel from copper sulfate bath electrolysis Manufactured on cylinder, rolled copper foil is to be repeated to manufacture with being heat-treated using the plastic working of stack.Requiring pliability Purposes in, mostly using rolled copper foil.
As the material of copper foil base material, except the tough pitch copper for the conductive pattern for being typically used as printed wiring board or oxygen-free copper etc. are high-purity Beyond the copper of degree, such as Erbium-doped can also be used to have Sn copper, Erbium-doped to have Ag copper, the copper alloy added with Cr, Zr or Mg etc., be added with The copper alloy of Ni and Si etc. the inferior series copper alloy of card etc.In addition, when term " copper foil " being used alone in this manual, also wrap Include copper alloy foil.In the case of the copper foil using copper alloy foil as high-frequency circuit board, or the resistance compared with copper The copper alloy foil that rate unobvious rise.
In addition, the thickness of slab of copper foil base material need not be particularly limited to, for example, 1~300 μm or 3~100 μm or 5 μm~ 70 μm or 6 μm~35 μm or 9 μm~18 μm.
(surface-treated layer)
It is preferred that on the surface of copper foil base material formed with based on selected from roughening treatment layer, antirust coat, refractory layer, silane coupled place Manage the surface-treated layer of the layer of one or more of layer.The surface-treated layer of the present invention can be formed as described to be connect with resin Face (M faces), the face (S faces) of side opposite with commissure (M faces) is also may be formed at, also may be formed at two sides.
Roughening treatment for example can be by forming roughening particle to carry out by copper or copper alloy.Roughening treatment can be fine thick Change is handled.In addition, plating processing also can be carried out after roughening treatment.By these roughening treatments, antirust treatment, it is resistance to heat treatment, Silane treatment, the impregnation to treatment fluid or plating handle formed surface-treated layer can also contain be selected from by Cu, Ni, Any of the group that Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, Ge are formed simple substance or any alloy above, or Organic matter.
In order to suppress influence of the ferromagnetism metal to transmission characteristic, and by Co, Ni, Fe's in the surface-treated layer of copper foil Total adhesion amount is controlled below specified quantitative as following, and is contained and do not shown that ferromagnetic Zn conducts are replaced at normal temperatures Point, it thus can further reduce high-frequency transmission loss.Therefore, surface-treated layer has Zn metal levels or the alloy treatment containing Zn Layer.In addition, the alloy treatment layer containing Zn is alternatively Cu-Zn alloy-layers.By being set to Cu-Zn alloy-layers, and with being set to Zn Single metal level is compared, and can improve heat resistance and chemical-resistant.
Surface-treated layer be using roughening treatment layer, antirust coat, refractory layer, any of silane coupled process layer and In the case of formation, the order of these layers is not particularly limited, such as also can form roughening treatment layer in copper foil surface, thick at this Change and Zn metal levels are set in process layer or contain Zn alloy treatment layer as antirust, refractory layer.In addition, also can be in Zn metal levels Or chromating layer is set on the alloy treatment layer containing Zn.And then it can also be set on chromating layer silane coupled Process layer.
(metal adhering amount)
On the surface treatment copper foil of the present invention, in surface-treated layer, Co, Ni, Fe total adhesion amount are controlled in 1000μg/dm2Below.For the surface treatment copper foil of the present invention, as described to as magnetic conductivity the reason for transmission loss Of a relatively high and relatively low conductance Co, Ni, Fe adhesion amount is controlled by, therefore can reduce high-frequency transmission loss.Table Total adhesion amount of Co, Ni, Fe in the process layer of face preferably 500 μ g/dm2Hereinafter, more preferably 300 μ g/dm2Hereinafter, it is and then more excellent Select 0 μ g/dm2(below the lower limit of quantitation value for representing analysis).
In the case where surface-treated layer includes roughening treatment layer, the adhesion amount of the Cu in the roughening treatment layer is preferred 0.10g/dm2Below.According to such a composition, high-frequency transmission loss can be further reduced.The adhesion amount of Cu in roughening treatment layer More preferably 0.09g/dm2Hereinafter, and then more preferably 0.08g/dm2Hereinafter, it is 0.04~0.08g/dm for typical case2。
The preferred 5mg/dm of adhesion amount of Zn in surface-treated layer2Below.According to such a composition, chemical-resistant improves, Heat resistance becomes good.The adhesion amount of Zn in surface-treated layer more preferably 4.5mg/dm2Hereinafter, and then more preferably 4mg/dm2With Under, it is 0.1~4.5mg/dm for typical case2。
The preferred 0.10g/dm of total adhesion amount of Cu, Zn, Co, Ni, Fe in surface-treated layer2Below.According to such a structure Into, can further reduce high-frequency transmission loss.Total adhesion amount of Cu, Zn, Co, Ni, Fe in surface-treated layer are more preferably 0.09g/dm2Hereinafter, and then preferred 0.08g/dm2Hereinafter, it is 0.04~0.08g/dm for typical case2。
(surface roughness Rz)
The main reason for roughness of copper foil surface is conductor losses, roughness is smaller, and transmission loss is more reduced.With regard to such a For viewpoint, surface treatment copper foil of the invention can by the surface roughness Rz JIS at least one surface control 2.2 μm with Under, and transmission loss can be reduced well.In addition, preferably less than 2.2 μm of the surface roughness Rz JIS on two surfaces.According to such a Form, can further reduce high-frequency transmission loss.
More preferably less than 1.5 μm of surface roughness Rz JIS, and then preferably less than 1.2 μm, it is 0.5~2.2 μ for typical m。
(surface area ratio)
Except the conventional surface roughness Rz managed for high frequency copper foil must be controlled inside and outside proper range, Also must be by more accurately expression and the three-dimensional table area phase of the contact area for the resin (dielectric medium) for influenceing high-frequency transmission loss Controlled for the ratio of bivariate table area in proper range.For such a viewpoint, surface treatment copper foil of the invention is by surface Handle layer surface using the three-dimensional table area measured by laser microscope relative to the ratio control of bivariate table area 1.0~ 1.9, even if so as to be used for high-frequency circuit board, also further suppress transmission loss well.Surface area ratio nothing in definition Method turns into the not value up to 1.0, if it exceeds 1.9, then have and produce the worry that high-frequency transmission loss becomes the problem of big.The surface area ratio It is preferred that 1.0~1.9, more preferably 1.0~1.6, and then more preferably 1.3~1.6.
(manufacture method of surface treatment copper foil)
In the present invention, it is preferred to the surface or two surfaces to copper foil base material (rolled copper foil or electrolytic copper foil) are implemented The roughening treatment of warty electro-deposition is carried out to the copper foil surface after pickling.Obtained and resin (dielectric medium) by roughening treatment Adhesion (peel strength).In the present invention, the roughening treatment for example can by selected from by Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, any of group that As, Ag, Sn, Ge are formed simple substance or it is any more than alloy plating or utilize organic matter Surface treatment etc. and carry out.Sometimes common copper facing etc. is carried out as the pretreatment before roughening, it is sometimes heat-resisting also for assigning Property, chemical-resistant and using the metal carry out plating as be roughened after surface treatment.In addition, at also can be without roughening Reason, and be selected from by any of Cu, Ni, Fe, Co, Zn, Cr, Mo, W, P, As, Ag, Sn, Ge group formed simple substance or The plating of alloy more than any.Thereafter, sometimes also for assign heat resistance, chemical-resistant and utilize the metal progress Plating is as surface treatment.In the case where carrying out roughening treatment, there is the advantages of being uprised with the contiguity intensity of resin.In addition, In the case of without roughening treatment, have the following advantages：The manufacturing step of surface treatment copper foil is simplified, so productivity carries Height, and cost can be reduced, in addition, roughness can be made to diminish.For rolled copper foil and electrolytic copper foil, also make the interior of processing sometimes Hold slightly different.By adjust such a copper foil surface plating handle liquid composition, plating time, current density, can control Total adhesion amount of Co, Ni, Fe in the surface-treated layer of invention, Zn metal levels are formed in surface-treated layer or contain Zn's Alloy treatment layer, and control surface processing layer surface using the three-dimensional table area measured by laser microscope relative to bivariate table The ratio of area, and then control surface roughness Rz JIS.
In addition, the electrolytic copper foil that surface roughness Rz turns into the scope can be made by following method.
＜ electrolyte forms ＞
Copper：90~110g/L
Sulfuric acid：90~110g/L
Chlorine：50~100ppm
Levelling agent 1 (double (3- sulfopropyls) disulphide)：10~30ppm
Levelling agent 2 (amines)：10~30ppm
The amines of following chemical formula can be used in the amines.
(in the chemical formula, R1And R2To select free hydroxyl alkyl, ether, aryl, aromatic series to substitute alkyl, unsaturated hydrocarbons Base in the group that base, alkyl are formed).
＜ manufacturing conditions ＞
Current density：70~100A/dm2
Electrolyte temperature：50~60 DEG C
Electrolyte linear speed：3~5m/sec
Electrolysis time：0.5~10 minute
The surface treatment copper foil of the present invention can be fitted on resin substrate from surface-treated layer side and manufacture laminate.Separately Outside, if necessary, can be further processed to the surface treatment copper foil and form circuit, printed wiring board etc. is thus manufactured. As long as resin substrate is the resin substrate with the characteristic that can be applied to printed wiring board or printed circuit board (PCB) etc., then not by special Limitation, such as rigid PWB purposes, paper base material phenol resin, paper base material epoxy resin, synthetic fibers cloth base material epoxy can be used Resin, glass cloth, glass cloth-paper composite base material epoxy resin, the glass cloth-glass non-woven fabric composite base material for being impregnated with fluororesin Epoxy resin and glass cloth base material epoxy resin etc., for soft printing substrate (FPC) purposes, it can be used polyester film or polyamides sub- Amine film, liquid crystal polymer (LCP) film, fluororesin and fluororesin-polyimides composite wood etc..In addition, liquid crystal polymer (LCP) Because dielectric loss is smaller, so the printed wiring board or printed circuit board (PCB) of high-frequency circuit purposes preferably use liquid crystal polymer (LCP) film.In addition, in the present invention, " printed wiring board " also includes the printed wiring board and printed circuit board (PCB) for being provided with part And printed base plate.In addition, more than 2 printed wiring boards of the invention can also be connected, and manufacture is connected with more than 2 and prints cloth The printed wiring board of line plate, in addition, also can be by the printed wiring board of at least one present invention and another printing cloth of the invention Line plate is not belonging to the printed wiring board of printed wiring board of the present invention and is attached, and is manufactured using such a printed wiring board E-machine.In addition, in the present invention, " copper circuit " also includes thin copper film.
On the method for fitting, in the case of for rigid PWB purposes, preparation makes resin impregnated in the base materials such as glass cloth And the prepreg for forming hardening of resin to semi-hardened state.Can be by the way that copper foil be overlapped on prepreg and carries out heating pressurization And carry out.In the case of for FPC, via bonding agent, or without using bonding agent at high temperature under high pressure by liquid crystal polymer or poly- The substrate layer pressure viscosity such as acid imide film is connected on copper foil, or polyimides predecessor is coated, dry, hardened, thus Laminate can be manufactured.
The laminate of the present invention can be used for various printed wiring boards (PWB) or printed circuit board (PCB), be not particularly limited.As Printed wiring board, such as the viewpoint of the number of plies of conductive pattern, can be applied to one side PWB, two sides PWB, (3 layers of multilayer PWB More than), for the viewpoint of the species of dielectric substrate material, it can be applied to rigid PWB, soft PWB (FPC), rigid-elastic PWB。
In addition, as another embodiment, the present invention or following surface treatment copper foil, it is at least one table Surface treatment copper foil of the face formed with surface-treated layer,
The surface-treated layer includes roughening treatment layer,
Total adhesion amount of Co, Ni, Fe in the surface-treated layer are 300 μ g/dm2Hereinafter, the surface-treated layer Alloy treatment layer with Zn metal levels or containing Zn, the surface treatment layer surface utilize the three-dimensional measured by laser microscope Surface area is 1.0~1.9 relative to the ratio of bivariate table area,
The surface roughness Rz JIS at least one surface are less than 2.2 μm,
On two surfaces formed with the surface-treated layer, the surface roughness Rz JIS on two surface are less than 2.2 μm.
In addition, as another embodiment, the present invention or a kind of surface treatment copper foil, it is at least one table Surface treatment copper foil of the face formed with surface-treated layer,
The surface-treated layer includes roughening treatment layer,
Total adhesion amount of Co, Ni, Fe in the surface-treated layer are 300 μ g/dm2Hereinafter, the surface-treated layer Alloy treatment layer with Zn metal levels or containing Zn, the surface treatment layer surface utilize the three-dimensional measured by laser microscope Surface area is 1.0~1.9 relative to the ratio of bivariate table area,
The surface roughness Rz JIS at least one surface are less than 2.2 μm,
The alloy treatment layer containing Zn is Cu-Zn alloy-layers.
In addition, as another embodiment, the present invention or following surface treatment copper foil, it is at least one table Surface treatment copper foil of the face formed with surface-treated layer,
The surface-treated layer includes roughening treatment layer,
Total adhesion amount of Co, Ni, Fe in the surface-treated layer are 300 μ g/dm2Hereinafter, the surface-treated layer Alloy treatment layer with Zn metal levels or containing Zn, the surface treatment layer surface utilize the three-dimensional measured by laser microscope Surface area is 1.0~1.9 relative to the ratio of bivariate table area,
The surface roughness Rz JIS at least one surface are less than 2.2 μm,
Total adhesion amount of Cu, Zn, Co, Ni, Fe in the surface-treated layer are 0.10g/dm2Below.
In addition, as another embodiment, the present invention or following surface treatment copper foil, it is at least one table Surface treatment copper foil of the face formed with surface-treated layer,
Total adhesion amount of Co, Ni, Fe in the surface-treated layer are 986 μ g/dm2Hereinafter, the surface-treated layer Alloy treatment layer with Zn metal levels or containing Zn, the surface treatment layer surface utilize the three-dimensional measured by laser microscope Surface area is 1.0~1.9 relative to the ratio of bivariate table area,
On two surfaces formed with the surface-treated layer, the surface roughness Rz JIS on two surface are less than 0.6 μm.
(Copper foil with carrier)
As the Copper foil with carrier of another embodiment of the invention, sequentially there is centre in the one or both sides of carrier Layer, very thin layers of copper.Moreover, the very thin layers of copper is the surface treatment copper foil as described an embodiment of the invention.
＜ carriers ＞
Be metal foil or resin film for carrier typical case available for the present invention, for example, with copper foil, copper alloy foil, nickel foil, Nickel alloy foil, iron foil, ferroalloy paper tinsel, stainless steel foil, aluminium foil, alloy foil, insulating resin film (such as polyimide film, liquid crystal Polymer (LCP) film, PET (PET) film, PA membrane, polyester film, fluororesin film etc.) form carry For.
As the carrier available for the present invention, preferably using copper foil.Its reason is：Copper foil is because conductance is higher, institute To become the easy intermediate layer formed thereafter, very thin layers of copper.It is in the form of rolled copper foil or electrolytic copper foil for carrier typical case There is provided.In general, electrolytic copper foil is copper is manufactured from copper sulfate bath electrolysis precipitation to the rotating cylinder of titanium or stainless steel, press It is to be repeated to manufacture with being heat-treated using the plastic working of stack to prolong copper foil.As the material of copper foil, except tough pitch copper or nothing Beyond the copper of the high-purities such as oxygen copper, such as the copper mixed with Sn, the copper mixed with Ag, the copper added with Cr, Zr or Mg etc. can also be used Alloy, the copper alloy for blocking inferior series copper alloy etc added with Ni and Si etc..
On the thickness of the carrier available for the present invention, it is not particularly limited, as long as appropriate be adjusted to playing as load Suitable thickness in the aspect of the effect of body, such as more than 5 μm can be set to.But if blocked up, production cost becomes Height, therefore generally preferably it is set to less than 35 μm.Therefore, it is 12~70 μm for the thickness typical case of carrier, is 18 for more typical ~35 μm.
In addition, for the present invention carrier can by as following control be formed intermediate layer side surface roughness Rz with And surface area ratio, and control surface processing after very thin layers of copper surface (being surface-treated layer surface) surface roughness Rz and Surface area ratio.
On the carrier for the present invention, the surface of the side in the formation intermediate layer of the carrier before control intermediate layer is formed in advance TD roughness (Rz) and surface area ratio it is also important.Specifically, the TD of the carrier before intermediate layer is formed surface roughness (Rz) it is 0.20~1.50 μm, preferably 0.20~1.00 μm, surface area ratio is 1.0~1.9, preferably 1.0~1.5.As this It copper foil, can in the following way make, that is, adjust the oil film equivalent of rolling oil and rolled, or carry out chemical etching etc Chemical grinding or phosphoric acid solution in electrolytic polishing, add specific additive in addition and manufacture electrolytic copper foil.By as above The TD of the copper foil of before processing surface roughness (Rz) and surface area ratio are set to the scope as stating, and can be easily at control The surface roughness (Rz) and surface area ratio of copper foil after reason.
In addition, calendering can be by being set to less than 13000~35000 to carry out by the oil film equivalent of following formula defined.
Oil film equivalent={ (calendering oil viscosity [cSt]) × (crossing plate speed [mPm]+roller peripheral speed [mpm]) }/{ (roller Sting angle [rad]) × (yield stress [kg/mm of material2])}
Calendering oil viscosity [cSt] is the dynamic viscosity at 40 DEG C.
In order that oil film equivalent is relatively low in the range of 13000~35000, following known method is used, i.e. make With the rolling oil of low viscosity, or slowed down plate speed etc..In addition, in order that oil film equivalent is in the range of 13000~35000 It is higher, use following known method, i.e. use highly viscous rolling oil, or improved plate speed etc..
In addition, the electrolytic copper foil that surface roughness Rz and surface area ratio turn into the scope can be carried out by the following method Make.The electrolytic copper foil can be used as carrier.
＜ electrolyte forms ＞
Copper：90~110g/L
Sulfuric acid：90~110g/L
Chlorine：50~100ppm
Levelling agent 1 (double (3- sulfopropyls) disulphide)：10~30ppm
Levelling agent 2 (amines)：10~30ppm
The amines of following chemical formula can be used in the amines.
(in the chemical formula, R1And R2To select free hydroxyl alkyl, ether, aryl, aromatic series to substitute alkyl, unsaturated hydrocarbons Base in the group that base, alkyl are formed).
＜ manufacturing conditions ＞
Current density：70~100A/dm2
Electrolyte temperature：50~60 DEG C
Electrolyte linear speed：3~5m/sec
Electrolysis time：0.5~10 minute (being adjusted according to the copper of precipitation thickness, current density)
In addition, also roughening treatment layer can be set on the surface of the side opposite with the surface of the side of the very thin layers of copper of setting of carrier. It can be used known method that the roughening treatment layer is set, also the roughening treatment layer can be set by the roughening treatment.Carrying The surface of the side opposite with the surface of the side of the very thin layers of copper of setting of body sets the situation of roughening treatment layer to have the following advantages that：To For carrier from when there is the face side of the roughening treatment layer to be laminated on the supporters such as resin substrate, carrier becomes difficult with resin substrate To peel off.
＜ intermediate layers ＞
Intermediate layer is set on carrier.Other layers can be also set between carrier and intermediate layer.Use in the present invention As long as intermediate layer is formed to be described as follows, it is not particularly limited, i.e., the step of Copper foil with carrier is laminated to insulated substrate before Very thin layers of copper is difficult to peel off from carrier, and on the other hand, become can be from carrier for very thin layers of copper after the step of being laminated to insulated substrate Peel off.For example, the present invention Copper foil with carrier intermediate layer also can contain be selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, It is one kind or two or more in the group that Al, Zn, these alloy, these hydrate, these oxide, organic matter are formed. In addition, intermediate layer is alternatively multilayer.
In addition, for example, intermediate layer can be formed in the following way：From carrier side formed with selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn form groups of elements a kind of element form single metal level or with selected from by Cr, Ni, Co, The alloy-layer that the one kind or two or more element for the groups of elements that Fe, Mo, Ti, W, P, Cu, Al, Zn are formed is formed, is formed on With the hydration of the one kind or two or more element selected from the groups of elements being made up of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn The layer that thing or oxide or organic matter are formed.
In addition, for example, intermediate layer can be formed in the following way：From carrier side formed with selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn form groups of elements a kind of element form single metal level or with selected from by Cr, Ni, Co, The alloy-layer that the one kind or two or more element for the groups of elements that Fe, Mo, Ti, W, P, Cu, Al, Zn are formed is formed, is formed on The single metal level that is formed with a kind of element selected from the groups of elements being made up of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, Or formed with the one kind or two or more element selected from the groups of elements being made up of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Alloy-layer.
In addition, known organic matter can be used as the organic matter in intermediate layer, additionally, it is preferred that using nitrogenous organic compound It is more than any of thing, organic compounds containing sulfur and carboxylic acid.For example, as specific organic compounds containing nitrogen, preferably use As the l, 2,3 triazole, carboxyl benzotriazole, N' of the triazole compounds with substituent, double (the BTA bases of N'- Methyl) urea, 1H-1,2,4- triazoles and 3- amino -1H-1,2,4- triazoles etc..
Organic compounds containing sulfur preferably uses mercaptobenzothiazoler, Vencide, trithiocyanuric acid and 2- Benzimidazole mercaptan etc..
As carboxylic acid, particularly preferably using monocarboxylic acid, wherein it is preferred that using oleic acid, linolenic acid and linolenic acid etc..
In addition, such as intermediate layer can sequentially be laminated nickel dam, nickel-phosphor alloy layer or nickel-cobalt alloy layer and contain on carrier Layers of chrome and form.The bonding force of nickel and copper higher than chromium and copper bonding force, therefore when peeling off very thin layers of copper, in very thin layers of copper and The interface of chrome-containing layer is peeling-off.In addition, for the nickel in intermediate layer, expect that it prevents copper component from carrier to very thin copper The barriering effect of layer diffusion.The adhesion amount of nickel in intermediate layer preferably 100 μ g/dm2Above and 40000 μ g/dm2Hereinafter, more preferably 100μg/dm2Above and 4000 μ g/dm2Hereinafter, more preferably 100 μ g/dm2Above and 2500 μ g/dm2Hereinafter, more preferably 100 μ g/ dm2Above and not up to 1000 μ g/dm2, the adhesion amount preferably 5 μ g/dm of the chromium in intermediate layer2Above and 100 μ g/dm2Below.Only In the case where one side sets intermediate layer, the antirust coats such as plating Ni layers preferably are set in the opposing face of carrier.The chromium in the intermediate layer Layer can be set by chromium plating or chromic acid salt treatment.
If the thickness in intermediate layer becomes too much, there is the thickness in intermediate layer to the very thin layers of copper surface after surface treatment The situation that surface roughness Rz and glossiness have an impact, therefore the thickness in the intermediate layer of the surface treatment layer surface of very thin layers of copper Spend preferably 1~1000nm, more preferably preferably 1~500nm, preferably 2~200nm, preferably 2~100nm, 3~60nm.In in addition, Interbed may also be arranged on the two sides of carrier.
The very thin layers of copper ＞ of ＜
Very thin layers of copper is set on the intermediate layer.Other layers can be also set between intermediate layer and very thin layers of copper.With the load The very thin layers of copper of body is the surface-treated metal material as an embodiment of the invention.The thickness of very thin layers of copper is not special Limitation, it is however generally that, it is thinner than carrier, for example, less than 12 μm.For typical case, be 0.5~12 μm, for more typical, be 1.5~ 5μm.In addition, before also very thin layers of copper being set on the intermediate layer, to reduce the pin hole of very thin layers of copper, and close using copper-phosphorus The pre- plating of gold.In pre- plating, cupric pyrophosphate plating solution etc. can be enumerated.In addition, very thin layers of copper may also be arranged on the two of carrier Face.Very thin layers of copper can be the layer containing copper alloy, or the layer being made up of copper alloy, very thin layers of copper can also contain organic matter Or inorganic matter.In addition, as very thin layers of copper, preferably using the very thin layers of copper that Cu concentration is more than 75mass%.Its reason is： Cu concentration is that the conductance of more than 75mass% very thin layers of copper is higher, is suitable for the purposes such as circuit.
In addition, the very thin layers of copper of the present invention is alternatively the very thin layers of copper formed under the following conditions.Its reason is：Pass through Smooth very thin layers of copper is formed, and controls the surface roughness Rz and surface area ratio of the surface-treated layer of Copper foil with carrier.
Electrolyte forms
Copper：80~120g/L
Sulfuric acid：80~120g/L
Chlorine：30~100ppm
Levelling agent 1 (double (3- sulfopropyls) disulphide)：10~30ppm
Levelling agent 2 (amines)：10~30ppm
The amines of following chemical formula can be used in the amines.
(in the chemical formula, R1And R2To select free hydroxyl alkyl, ether, aryl, aromatic series to substitute alkyl, unsaturated hydrocarbons Base in the group that base, alkyl are formed).
Manufacturing condition
Current density：70~100A/dm2
Electrolyte temperature：50~65 DEG C
Electrolyte linear speed：1.5~5m/sec
Electrolysis time：0.5~10 minute (being adjusted according to the copper of precipitation thickness, current density)
Hereinafter, the example of the manufacturing step of the printed wiring board of several Copper foil with carrier using the present invention is disclosed.
In an embodiment of the manufacture method of the printed wiring board of the present invention, comprise the following steps：Prepare this hair The step of bright Copper foil with carrier and insulated substrate；The step of Copper foil with carrier and insulated substrate are laminated；And will The Copper foil with carrier and insulated substrate are after very thin layers of copper side and insulated substrate in a manner of to being laminated, by peeling off institute The step of stating the carrier of Copper foil with carrier and form copper clad laminate, thereafter, pass through semi-additive process, improve semi-additive process, part Either method in addition process and subtractive process and the step of form circuit.Insulated substrate can also be set to add the exhausted of internal layer circuit Edge substrate.
In the present invention, so-called semi-additive process refers to carry out relatively thin electroless plating on insulated substrate or copper foil inculating crystal layer Apply, after forming pattern, use plating and the method for etching and forming conductive pattern.
Therefore, in an embodiment using the manufacture method of the printed wiring board of the invention of semi-additive process, bag Include following steps：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；By the Copper foil with carrier and insulated substrate The step of being laminated；It is laminated the Copper foil with carrier and the step that after insulated substrate, the carrier of the Copper foil with carrier is peeled off Suddenly；By using the etchant solutions such as acid etching or plasma-based the methods of, the very thin layers of copper peeled off the carrier and exposed is whole The step of removal；The step of through hole and/or blind hole is being set by etching the resin removed the very thin layers of copper to expose Suddenly；The step of removing glue Slag treatment being carried out for the region containing the through hole and/or blind hole；For containing the resin and described The region of through hole and/or blind hole sets the step of electroless plating；On the electroless plating set plating resist application the step of；To institute Plating resist application is stated to be exposed, thereafter will be formed circuit region plating resist application remove the step of；Eliminating the plating resist The step of region that the formation of application has the circuit sets electro deposition；The step of plating resist application is removed；And pass through Fast-etching etc., the step of electroless plating in the region that will be present in being formed beyond the region of the circuit removes.
In another embodiment using the manufacture method of the printed wiring board of the invention of semi-additive process, including such as Lower step：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；The Copper foil with carrier and insulated substrate are carried out The step of lamination；It is laminated the step of Copper foil with carrier is with after insulated substrate, the carrier of the Copper foil with carrier is peeled off；It is logical The methods of crossing etching or the plasma-based using etchant solutions such as acid, the very thin layers of copper peeled off the carrier and exposed all is removed Step；Surface for the very thin layers of copper to be removed to the resin to expose by etching, the step of electroless plating is set； On the electroless plating set plating resist application the step of；The plating resist application is exposed, the area of circuit will be formed thereafter The step of plating resist application in domain removes；In the region for the formation circuit for eliminating the plating resist application, electro deposition is set Step；The step of plating resist application is removed；And by fast-etching etc., it will be present in being formed beyond the region of the circuit Region electroless plating and very thin layers of copper remove the step of.
In the present invention, so-called improvement semi-additive process refers to laminated metal foil on the insulating layer, is protected by plating resist application Inverter circuit forming portion, after the copper facing by being electrolysed plating progress circuit forming portion thickens, resist is removed, utilizes (quick) etching The metal foil beyond the circuit forming portion is removed, the method for thus forming circuit on the insulating layer.
Therefore, in an embodiment of the manufacture method using the printed wiring board of the invention for improving semi-additive process In, comprise the following steps：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；By the Copper foil with carrier and insulation The step of substrate is laminated；The Copper foil with carrier is laminated with after insulated substrate, the carrier of the Copper foil with carrier is peeled off The step of；Very thin layers of copper that the carrier is peeled off and exposed sets through hole and/or blind hole with insulated substrate the step of；For The step of removing glue Slag treatment being carried out containing the region of the through hole and/or blind hole；For the area containing the through hole and/or blind hole Domain sets the step of electroless plating；The step of plating resist application is set on the very thin layers of copper surface that the carrier is peeled off and exposed； After setting the plating resist application, by being electrolysed the step of plating forms circuit；The step of plating resist application is removed；And pass through Fast-etching, the step of the very thin layers of copper exposed by the removal plating resist application is removed.
In addition, it is alternatively another Copper foil with carrier from very thin layers of copper side circuit is formed on the resin bed the step of It is fitted on the resin bed, the step of forming the circuit using the Copper foil with carrier for being fitted in the resin bed.In addition, Another Copper foil with carrier being fitted on the resin bed is alternatively the Copper foil with carrier of the present invention.In addition, in the resin The step of forming circuit on layer also by semi-additive process, subtractive process, part addition process or can improve any of semi-additive process Method and carry out.In addition, the Copper foil with carrier in the circuit forming surface also can be on the surface of the carrier of the Copper foil with carrier With substrate or resin bed.
In another embodiment using the manufacture method for the printed wiring board of the invention for improving semi-additive process, bag Include following steps：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；By the Copper foil with carrier and insulated substrate The step of being laminated；It is laminated the Copper foil with carrier and the step that after insulated substrate, the carrier of the Copper foil with carrier is peeled off Suddenly；In the very thin layers of copper that the carrier is peeled off and exposed set plating resist application the step of；The plating resist application is exposed Light, thereafter will be formed circuit region plating resist application remove the step of；Eliminating the formation electricity of the plating resist application The region on road sets the step of electro deposition；The step of plating resist application is removed；By fast-etching etc., shape will be present in The step of electroless plating in the region beyond into the region of the circuit and very thin layers of copper remove.
In the present invention, so-called part addition process be directed to be provided with conductor layer form substrate, optionally giving a farfetched interpretation has through hole Or catalyst core is assigned on the substrate that forms of the hole of via hole, it is etched and forms conductor circuit, welding resistance is optionally set After agent or plating resist application, handled by electroless plating, and on the conductor circuit, through hole or via hole etc. are thickened, Thus the method for manufacturing printed wiring board.
Therefore, in an embodiment using the manufacture method of the printed wiring board of the invention of part addition process, Comprise the following steps：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；By the Copper foil with carrier and insulation base The step of plate is laminated；The Copper foil with carrier is laminated with after insulated substrate, the carrier of the Copper foil with carrier is peeled off Step；The very thin layers of copper peeled off the carrier and exposed on insulated substrate with setting through hole and/or blind hole the step of；For containing There is the step of region of the through hole and/or blind hole carries out removing glue Slag treatment；Assigned to the region containing the through hole and/or blind hole The step of giving catalyst core；The step of etching resist is set on the very thin layers of copper surface peeled off the carrier and exposed；To described The step of etching resist to be exposed, and forming circuit pattern；By using the etchant solutions such as acid etching or plasma-based the methods of, The step of very thin layers of copper and the catalyst core are removed and form circuit；The step of etching resist is removed； By using the etchant solutions such as acid etching or plasma-based the methods of the very thin layers of copper and the catalyst core removed and exposed The insulated substrate surface, solder resist is set or the step of plating resist application；And it is being not provided with the solder resist or plating resist application Region set electroless plating the step of.
In the present invention, so-called subtractive process refers to by etching etc., by the unnecessary portion of the copper foil on copper clad laminate It is selectively removed, and the method for forming conductive pattern.
Therefore, in an embodiment using the manufacture method of the printed wiring board of the invention of subtractive process, including Following steps：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；The Copper foil with carrier is entered with insulated substrate The step of row lamination；It is laminated the step of Copper foil with carrier is with after insulated substrate, the carrier of the Copper foil with carrier is peeled off； The very thin layers of copper peeled off the carrier and exposed sets through hole and/or blind hole with insulated substrate the step of；For containing described The region of through hole and/or blind hole carries out the step of removing glue Slag treatment；For the region containing the through hole and/or blind hole, nothing is set The step of electrodeposited coating；The step of electro deposition is set on the surface of the electroless plating；In the electro deposition and/or the pole The surface of thin copper layer sets the step of etching resist；The step of being exposed to the etching resist, and forming circuit pattern；It is logical The methods of crossing etching or the plasma-based using etchant solutions such as acid, the very thin layers of copper and the electroless plating and the electrolysis are plated Layer removes, and the step of form circuit；And the step of removing the etching resist.
In another embodiment using the manufacture method of the printed wiring board of the invention of subtractive process, including it is as follows Step：The step of preparing the Copper foil with carrier and insulated substrate of the present invention；The Copper foil with carrier and insulated substrate are subjected to layer The step of pressure；It is laminated the step of Copper foil with carrier is with after insulated substrate, the carrier of the Copper foil with carrier is peeled off；Shelling The step of very thin layers of copper exposed from the carrier sets through hole and/or blind hole with insulated substrate；For containing the through hole And/or the region of blind hole carries out the step of removing glue Slag treatment；For the region containing the through hole and/or blind hole, electroless plating is set The step of layer；The step of mask being formed on the surface of the electroless plating；On the surface for the electroless plating for not forming mask The step of electro deposition is set；The step of etching resist is set on the surface of the electro deposition and/or the very thin layers of copper；It is right The etching resist is exposed, and the step of form circuit pattern；By using the etching of the etchant solutions such as acid or plasma-based etc. The step of method, the very thin layers of copper and the electroless plating being removed, and forming circuit；And remove the etching resist Step.
Through hole is set and/or the step of blind hole and subsequent de-smear step also can be without.
Herein, the concrete example of the manufacture method of the printed wiring board of the Copper foil with carrier using the present invention is carried out in detail Explanation.In addition, this is illustrated exemplified by sentencing the Copper foil with carrier with the very thin layers of copper formed with roughening treatment layer, but not It is limited to this, even with the Copper foil with carrier with the very thin layers of copper for not forming roughening treatment layer, also can similarly carries out following Printed wiring board manufacture method.
First, prepare with the Copper foil with carrier (the 1st layer) in very thin layers of copper of the surface formed with roughening treatment layer.
Secondly, the painting erosion resistant agent on the roughening treatment layer of very thin layers of copper, it is exposed, develops, and resist is etched For given shape.
Secondly, after forming the coating of circuit, resist is removed, is consequently formed the circuit coating of given shape.
Secondly, set in a manner of covering circuit coating (in the way of burying circuit coating) in very thin layers of copper and bury resin And laminated resin layer, then make another Copper foil with carrier (the 2nd layer) from very thin layers of copper side bonds.
Secondly, the Copper foil with carrier from the 2nd layer peels off carrier.
Secondly, laser beam drilling is carried out in the ad-hoc location of resin bed, circuit coating is exposed and is formed blind hole
Secondly, it is embedded to copper to blind hole and forms guide hole filler.
Secondly, on guide hole filler, circuit coating is formed in the above described manner.
Secondly, the Copper foil with carrier from the 1st layer peels off carrier.
Secondly, the very thin layers of copper on two surfaces is removed by fast-etching, and makes the surface of the circuit coating in resin bed Expose.
Secondly, projection is formed on the circuit coating in resin bed, copper pillar is formed on the solder.Make in this way Use the printed wiring board of the Copper foil with carrier of the present invention.
Described (the 2nd layer) Copper foil with carrier that the present invention can be used of another Copper foil with carrier, it is possible to use conventional is attached Carrier copper foil, common copper foil also can be used.In addition, 1 layer or multilayer also can be further formed on described 2nd layer of circuit Circuit, also these can be carried out by any of semi-additive process, subtractive process, part addition process or improvement semi-additive process method Circuit is formed.
The Copper foil with carrier of the present invention is preferably the aberration on the control pole thin copper layer surface in a manner of meeting following (1). " aberration on very thin layers of copper surface " so-called in the present invention is the aberration on the surface for representing very thin layers of copper, or is being implemented with roughening treatment The aberration of the surface treatment layer surface is represented in the case of etc. various surface treatments.That is, Copper foil with carrier of the invention is preferably The aberration on the roughening treatment surface of control pole thin copper layer in a manner of meeting following (1).In addition, in the surface treatment gold of the present invention So-called " roughening treatment surface " refers to after roughening treatment in category material, carries out setting refractory layer, antirust coat, weatherable layer etc. Surface treatment in the case of, carry out the surface of the surface-treated metal material after the surface treatment (very thin layers of copper).In addition, in table In the case of very thin layers of copper of the face processing metal material for Copper foil with carrier, so-called " roughening treatment surface " refers in roughening treatment Afterwards, in the case of the surface treatment for carrying out setting refractory layer, antirust coat, weatherable layer etc., after carrying out the surface treatment The surface of very thin layers of copper.
(1) aberration on very thin layers of copper surface, the aberration Δ E*ab based on JIS Z8730 are more than 45.
Herein, aberration Δ L, Δ a, Δ b are to be utilized respectively colour difference meter and determine, and plus black/white/red green/yellow blue, and are made The overall target being indicated with the L*a*b colour systems based on JIS Z8730, and with Δ L：White black, Δ a：Red green, Δ b：It is yellow Blue mode is indicated.In addition, Δ E*ab is to be represented using these aberration with following formula.
Current density when described aberration can be by making to form very thin layers of copper uprises, and becomes the copper concentration in plating solution It is low, the line flow velocity of plating solution is uprised and is adjusted.
In addition, described aberration also can by roughening treatment is implemented to the surface of very thin layers of copper come set roughening treatment layer and It is adjusted., can be by using containing copper and selected from being made up of nickel, cobalt, tungsten, molybdenum in the case where setting roughening treatment layer The electrolyte of more than a kind of element in group, and current density is higher than conventional current density (such as 40~60A/dm2), make Processing time is shorter than conventional processing time (such as 0.1~1.3 second) and is adjusted.It is not provided with slightly on the surface of very thin layers of copper In the case of changing process layer, it can be reached by following manner, i.e. use the plating that Ni concentration is set to more than 2 times of other elements Bath, with less than conventional current density (0.1~1.3A/dm2), and longer (20 seconds~40 seconds) will be set as processing time, and Ni alloy plateds are carried out in very thin layers of copper or refractory layer or antirust coat or the surface of chromating layer or silane coupled process layer (such as Ni-W alloy plateds, Ni-Co-P alloy plateds, Ni-Zn alloy plateds) processing.
On the aberration on very thin layers of copper surface, the aberration Δ E*ab if based on JIS Z8730 is more than 45, then for example exists During the very thin layers of copper circuit forming surface of Copper foil with carrier, the contrast of very thin layers of copper and circuit becomes distinct, and its result is, depending on recognizing Property become good, and can precision carry out the position alignment of circuit well.The aberration Δ based on JIS Z8730 on very thin layers of copper surface E*ab preferably more than 50, more preferably more than 55, and then more preferably more than 60.
As above in the case of the aberration on control pole thin copper layer surface, become distinct with the contrast of circuit coating, depending on recognizing Property become good.Therefore, in the manufacturing step of printed wiring board as mentioned, can precision well ad-hoc location formed circuit Coating.In addition, according to the manufacture method of printed wiring board as mentioned, turn into the composition that circuit coating is embedded in resin bed, because This, such as in the very thin layers of copper of removal using fast-etching, circuit coating is protected by resin bed, and its shape is protected Hold, thus become easily to form fine circuits.In addition, circuit coating is protected by resin bed, therefore resistance to migration improves, and good The conducting of the wiring of suppression circuit well.Therefore, become easily to form fine circuits.In addition, removed by fast-etching During very thin layers of copper, the exposed surface of circuit coating turns into the shape from resin bed depression, therefore becomes easy on the circuit coating Projection is formed, and then becomes thereon easily to form copper pillar, and manufacture efficiency raising.
In addition, known resin, prepreg can be used in embedment resin (RESIN).Such as BT (BMIs can be used Triazine) resin or as containing be soaked with BT resins glass cloth prepreg, aginomoto fine chemistry (Ajinomoto Fine- Techno) the ABF films or ABF of limited company's manufacture.In addition, this specification institute can be used in the embedment resin (RESIN) The resin bed and/or resin and/or prepreg of record.
In addition, Copper foil with carrier used in the first layer also can have substrate or tree on the surface of the Copper foil with carrier Lipid layer.By with the substrate or resin bed, and Copper foil with carrier used in first layer is supported, so as to which fold becomes to be difficult to produce It is raw, therefore have the advantages of productivity raising.Furthermore for the substrate or resin bed, as long as to play support described first The substrate or resin bed of the effect of Copper foil with carrier used in layer, then can be used whole substrate or resin bed.Such as it can make With the carrier described in present application specification, prepreg, resin bed or known carrier, prepreg, resin bed, metallic plate, Metal foil, the plate of inorganic compound, the paper tinsel of inorganic compound, the plate of organic compound, the paper tinsel of organic compound are as the base Plate or resin bed.
[embodiment]
Prepare the rolled copper foil (C1100 of JX ore deposit day, stones day metal company manufacture) of 18 μm of thickness or the electricity of 18 μm of thickness Copper foil is solved as embodiment 1~10 and the copper foil base material of comparative example 1~6.
Secondly, plating is carried out under conditions of shown in table 1~2 as surface treatment.It is to passing through on embodiment 1~4 The precipitation face (Rz0.6 μm) of electrolytic copper foil made by methods described is surface-treated, on embodiment 5~7 and comparative example 1st, 4~6, it is that the rotating cylinder face (Rz1.5 μm) of the electrolytic copper foil is surface-treated.On comparative example 2,3, using not containing The electrolyte of levelling agent is surface-treated to the precipitation face (Rz2.0 μm) of made electrolytic copper foil.In addition, embodiment 8~ 10 be to be surface-treated to controlling for the rolled copper foil of specific surface roughness.Table 1 represents the liquid group of each plating solution 1~10 Into, pH value, temperature, current density.Table 2 represents to form with described bath and the time sequentially carries out the feelings of plating processing 1~3 Condition.In addition, ensure heat resistance by plating Zn, plating Ni or these alloy plated and chromic acid salt treatment after the plating, and then Peel strength is improved by silane-coating coupling agent.
The application conditions of silane coupler are as described below.
3- methacryloxypropyl trimethoxy silanes
Silane concentration：0.6vol% (remainders：Water)
Treatment temperature：30~40 DEG C
Processing time：5 seconds
Drying after silane treatment：100 DEG C × 3 seconds
In addition, the surface treatment of embodiment 1,9 and following embodiments 11 is handled equivalent to smooth plating and (is not roughened The surface treatment of processing), the surface treatment in embodiment in addition and comparative example is equivalent to roughening treatment.
In addition, prepare base material of the following described Copper foil with carrier as embodiment 11~15.
On embodiment 11~13, the electrolytic copper foil (HLP of JX ore deposit day, stones day metal company manufacture of 18 μm of thickness of preparation Paper tinsel) carrier is used as, on embodiment 14, the electrolytic copper foil (JTC of JX ore deposit day, stones day metal company manufacture of 18 μm of thickness of preparation Paper tinsel) carrier is used as, on embodiment 15, (JX ore deposit day, stones day metal company manufactures the rolled copper foil of 18 μm of thickness of preparation C1100) it is used as carrier.And under the following conditions, on embodiment 11~13, in being formed on the surface of the precipitation surface side of carrier Interbed, on embodiment 14, intermediate layer is formed on the surface of the rotating cylinder face of carrier (gloss surface side), on embodiment 15, is being carried The surface of body forms intermediate layer.Thereafter, in embodiments, very thin layers of copper is formed on the surface in intermediate layer.In addition, carrier be In the case of needing, by described method and control the surface intermediate layer to form intermediate layer side formed before surface surface it is thick Rugosity Rz and surface area ratio.
Embodiment 11
＜ intermediate layers ＞
(1) Ni layers (plating Ni)
For carrier, electroplated under the following conditions on the continuous plating wiring of roll-to-roll type, be consequently formed 1000 μ g/ dm2Adhesion amount Ni layers.Specific plating condition is recorded in following.
Nickel sulfate：270~280g/L
Nickel chloride：35~45g/L
Nickel acetate：10~20g/L
Boric acid：30~40g/L
Polishing material：Saccharin, butynediols etc.
Lauryl sodium sulfate：55~75ppm
PH value：4~6
Bath temperature：55~65 DEG C
Current density：10A/dm2
(2) Cr layers (electrolytic chromate processing)
Secondly, the Ni layer surfaces formed in (1) are washed and pickling after, then by under the following conditions in roller To carrying out electrolytic chromate processing on the continuous plating wiring of roll shape, and make 11 μ g/dm2The Cr layers of adhesion amount be attached to Ni layers On.
1~10g/L of potassium bichromate, zinc 0g/L
PH value：7~10
Liquid temperature：40~60 DEG C
Current density：2A/dm2
The very thin layers of copper ＞ of ＜
Secondly, the Cr layer surfaces formed in (2) are washed and pickling after, then by under the following conditions in roller To being electroplated on the continuous plating wiring of roll shape, and the very thin layers of copper of 1.5 μm of thickness is formed on Cr layers, and make appendix body pole Thin copper foil.
Copper concentration：90~110g/L
Sulfuric acid concentration：90~110g/L
Chloride ion concentration：50~90ppm
Levelling agent 1 (double (3- sulfopropyls) disulphide)：10~30ppm
Levelling agent 2 (amines)：10~30ppm
In addition, it is used as levelling agent 2 using following amines.
(in the chemical formula, R1And R2To select free hydroxyl alkyl, ether, aryl, aromatic series to substitute alkyl, unsaturated hydrocarbons Base in the group that base, alkyl are formed).
Electrolyte temperature：50~80 DEG C
Current density：100A/dm2
Electrolyte linear speed：1.5~5m/sec
Embodiment 12
＜ intermediate layers ＞
(1) Ni-Mo layers (nickel-molybdenum alloy coating)
For carrier, electroplated under the following conditions on the continuous plating wiring of roll-to-roll type, be consequently formed 3000 μ g/ dm2Adhesion amount Ni-Mo layers.Specific plating condition is recorded in following.
(liquid composition) sulfuric acid Ni hexahydrates：50g/dm3, sodium molybdate dihydrate：60g/dm3, sodium citrate：90g/dm3
30 DEG C of (liquid temperature)
(current density) 1~4A/dm2
(conduction time) 3~25 seconds
The very thin layers of copper ＞ of ＜
Very thin layers of copper is formed on Ni-Mo layers formed in (1).The thickness of very thin layers of copper is set to 2 μm, except this with Outside, very thin layers of copper is being formed under the same conditions with embodiment 11.
Embodiment 13
＜ intermediate layers ＞
(1) Ni layers (plating Ni)
Ni layers are being formed under the same conditions with embodiment 11.
(2) organic matter layer (organic matter layer formation processing)
Secondly, the Ni layer surfaces formed in (1) are washed and pickling after, then under the following conditions, will contain 40 DEG C of the liquid temperature of 1~30g/L of concentration carboxyl benzotriazole (CBTA) and the aqueous solution of pH value 5 carries out 20 to Ni layer surfaces~ 120 seconds spray washings, are consequently formed organic matter layer.
The very thin layers of copper ＞ of ＜
Very thin layers of copper is formed on organic matter layer formed in (2).The thickness of very thin layers of copper is set to 3 μm, except this with Outside, very thin layers of copper is being formed under the same conditions with embodiment 11.
Embodiment 14,15
＜ intermediate layers ＞
(1) Co-Mo layers (cobalt molybdenum alloy plating)
For carrier, electroplated under the following conditions on the continuous plating wiring of roll-to-roll type, be consequently formed 4000 μ g/ dm2Adhesion amount Co-Mo layers.Specific plating condition is recorded in following.
(liquid composition) sulfuric acid Co：50g/dm3, sodium molybdate dihydrate：60g/dm3, sodium citrate：90g/dm3
30 DEG C of (liquid temperature)
(current density) 1~4A/dm2
Between (Tong electricity Time) 3~25 seconds
The very thin layers of copper ＞ of ＜
Very thin layers of copper is formed on Co-Mo layers formed in (1).In embodiment 14, the thickness of very thin layers of copper is set For 3 μm, in embodiment 15, the thickness of very thin layers of copper is set to 5 μm, in addition, with embodiment 11 under the same conditions Form very thin layers of copper.
[table 1]
[table 2]
For and the embodiment made and each sample of comparative example, various evaluations are carried out as following by the mode.
The measure ＞ of ＜ adhesion amounts
On the measure of the various metal adhering amounts beyond the Cu of surface-treated layer, make 50mm × 50mm copper foil surface Epithelium is dissolved in mixing HNO3The solution that (2 weight %) forms with HCl (5 weight %), utilizes ICP emission spectrographic analysis devices (Seiko electronics nanosecond science and technology limited company manufactures, SFC-3100) quantifies to the metal concentration in the solution, and pushes away Lead amount of metal (the μ g/dm for calculating per unit area2).Now, will not with the metal adhering amount in the face opposite with the face to be determined Mixed mode, is optionally covered, and is analyzed.In addition, measure be for carry out described plating Zn, plating Co, plating Ni, The sample after Fe or these alloy plated and chromic acid salt treatment and then silane coupled processing is plated to carry out.On surface-treated layer Cu adhesion amount measure, be to subtract to survey by methods described from the weight of the surface treatment copper foil of 100mm × 100mm sizes The per unit of copper foil before the adhesion amount of the various metals in addition to Cu of the per unit area obtained and surface treatment The weight of area and obtain.
＜ surface roughnesses Rz measure ＞
The contact roughmeter SP-11 manufactured using limited company of little Ban research institutes, according to JIS B0601- 1994, determine 10 mean roughness (Rz) for surface treatment face.In measure datum length 0.8mm, evaluation length 4mm, cut Only under conditions of value 0.25mm, transporting velocity 0.1mm/sec, change locates progress 10 times, by being averaged for 10 measured values Value is set to surface roughness Rz value.In addition, for each electrolytic copper foil and rolled copper foil used in embodiment and comparative example, Also the roughness Rz before surface treatment is measured in advance.In addition, the measure of 10 mean roughness is to be directed to TD directions (copper The width (direction vertical with the copper foil direction of advance in copper foil manufacture device) of paper tinsel) and carry out.
The measure ＞ of ＜ surface area ratios
It is the laser microscope manufactured using Olympus (Olympus) limited company on three-dimensional table area LEXTOLS4000 (optical maser wavelength 405nm, Wei Fen Gan Wataru modes), for the two-dimensional surface in the precipitation face of surface treatment copper foil Product is 66455 μm2Region be measured.Value obtained by measured three-dimensional table area divided by bivariate table area is set to surface Product ratio.
The measure ＞ of ＜ transmission loss
For 18 μm of each sample of thickness, it is allowed to and commercially available liquid crystal polymer resin (Kuraray (Kuraray) (share) The Vecstar CTZ-50 μm of manufacture) fitting after, by etching, by characteristic impedance turn into 50 Ω in a manner of form microwave transmission Band circuit, the Network Analyzer-HP8720C manufactured using Hewlett-Packard Corporation, determines transmission coefficient, and obtains under frequency 20GHz Transmission loss.On the evaluation of the transmission loss under frequency 20GHz, ◎ will be set to less than 5.0dB/10cm, will be 5.0dB/ 10cm is set to zero less than 6.0dB/10cm, more than 6.0dB/10cm is set to ×.The size of transmission loss is by being made Relative dielectric constant, dielectric loss tangent and the thickness of resin are influenceed, so will be to typically being made with printed wiring board Copper foil (copper foil used in comparative example 2) has a case that obvious transmission loss reducing effect is set to the judgement base It is accurate.
Result of the test is shown in table 3.
[table 3]
(evaluation result)
On embodiment 1~15, total adhesion amount of Co, Ni, Fe in surface-treated layer are 1000 μ g/dm2Hereinafter, It is 1.0~1.9 that surface-treated layer, which is respectively provided with Zn metal levels or the alloy treatment layer containing Zn, surface area ratio, surface roughness Rz JIS are less than 2.2 μm.Therefore, the transmission loss of embodiment 1~15 is suppressed well.
Comparative example 1 is because surface area ratio is more than 1.9, so transmission loss is larger.
Comparative example 2 because surface roughness Rz JIS are more than 2.2 μm, surface area ratio more than 1.9, so transmission loss compared with Greatly.
Comparative example 3 is because surface roughness Rz JIS are more than 2.2 μm, so transmission loss is larger.
Comparative example 4~6 is due to being that the plating processing 3 of embodiment 7 is changed into the plating containing Co, Ni, Fe to handle, and table Total adhesion amount of Co, Ni, Fe in the process layer of face are more than 1000 μ g/dm2, so the transmission loss of comparative example 4~6 is more than in fact Apply example 7.
Co, Ni, Fe of embodiment and comparative example total adhesion amount, the relation with surface roughness Rz are represented in Fig. 1 Chart.Co, Ni, Fe of expression embodiment and comparative example total adhesion amount and three-dimensional table area are relative to two dimension in fig. 2 The chart of the relation of the ratio of surface area.Represent in figure 3 Co, Ni, Fe, Cu, Zn of embodiment and comparative example total adhesion amount, With the chart of the relation of transmission loss.

Claims (25)

1. a kind of surface treatment copper foil, at least one surface formed with surface-treated layer,
Total adhesion amount of Co, Ni, Fe in the surface-treated layer are 1000 μ g/dm2Hereinafter, the surface-treated layer has Zn metal levels or the alloy treatment layer containing Zn, the surface treatment layer surface utilize the three-dimensional surface measured by laser microscope Product is 1.0~1.9 relative to the ratio of bivariate table area,
The surface roughness Rz JIS at least one surface are less than 2.2 μm.
2. surface treatment copper foil according to claim 1, wherein Co, Ni, Fe's in the surface-treated layer is total attached The amount of wearing is 500 μ g/dm2Below.
3. surface treatment copper foil according to claim 2, wherein Co, Ni, Fe's in the surface-treated layer is total attached The amount of wearing is 300 μ g/dm2Below.
4. surface treatment copper foil according to claim 3, wherein Co, Ni, Fe's in the surface-treated layer is total attached The amount of wearing is 0 μ g/dm2。
5. surface treatment copper foil according to claim 1, wherein the surface roughness Rz JIS on two surfaces be 2.2 μm with Under.
6. surface treatment copper foil according to claim 1, wherein the surface-treated layer includes roughening treatment layer.
7. surface treatment copper foil according to claim 6, wherein the adhesion amount of the Cu in the roughening treatment layer is 0.10g/dm2Below.
8. surface treatment copper foil according to claim 6, wherein in the surface-treated layer, in the roughening treatment layer On be provided with the Zn metal levels or the alloy treatment layer containing Zn.
9. surface treatment copper foil according to claim 1, wherein the alloy treatment layer containing Zn is Cu-Zn alloys Layer.
10. surface treatment copper foil according to claim 1, wherein the adhesion amount of the Zn in the surface-treated layer is 5mg/ dm2Below.
11. surface treatment copper foil according to claim 1, wherein in the surface-treated layer, in the Zn metal levels Or it is provided with chromating layer on the alloy treatment layer containing Zn.
12. surface treatment copper foil according to claim 11, wherein being provided with silane idol on the chromating layer Join process layer.
13. surface treatment copper foil according to claim 1, wherein Cu, Zn, Co, Ni, Fe in the surface-treated layer Total adhesion amount is 0.10g/dm2Below.
14. the surface treatment copper foil according to any one of claim 1 to 13, it is used for soft printing wiring plate.
15. the surface treatment copper foil according to any one of claim 1 to 13, it is used for more than 5GHz high-frequency electrical roadbed Plate.
16. a kind of laminate, it is by the surface treatment copper foil and resin substrate according to any one of claim 1 to 13 It is laminated and is manufactured.
17. a kind of printed wiring board, it is to be used as material using laminate according to claim 16.
18. a kind of e-machine, it uses the printed wiring board described in good grounds claim 17.
19. a kind of Copper foil with carrier, sequentially there is intermediate layer, very thin layers of copper, the very thin layers of copper in the one or both sides of carrier For the surface treatment copper foil according to any one of claim 1 to 13.
20. Copper foil with carrier according to claim 19, wherein the carrier one side sequentially have the intermediate layer, The very thin layers of copper, there is roughening treatment layer in the another side of the carrier.
21. a kind of laminate, it is to be laminated the Copper foil with carrier according to claim 19 or 20 with resin substrate And manufacture.
22. a kind of printed wiring board, it is manufactured using laminate according to claim 21.
23. a kind of e-machine, it uses the printed wiring board described in good grounds claim 22.
24. a kind of manufacture method of printed wiring board, it comprises the following steps：
The step of preparing the Copper foil with carrier and insulated substrate according to claim 19 or 20；
The step of Copper foil with carrier and insulated substrate are laminated；
After the Copper foil with carrier and insulated substrate are laminated, the step of by by the carrier stripping of the Copper foil with carrier And metal-coated laminated board is formed, thereafter, pass through any in semi-additive process, subtractive process, part addition process or improvement semi-additive process Kind of method and the step of form circuit.
25. a kind of manufacture method of printed wiring board, it comprises the following steps：
In the very thin layers of copper side surface of the Copper foil with carrier according to claim 19 or 20 or the carrier side surface The step of forming circuit；
In the very thin layers of copper side surface of the Copper foil with carrier or the carrier side surface in a manner of burying the circuit The step of forming resin bed；
On the resin bed formed circuit the step of；
After forming circuit on the resin bed, the step of the carrier or the very thin layers of copper are peeled off；And
After the carrier or the very thin layers of copper are peeled off, the very thin layers of copper or the carrier are removed, thus make to be formed The step of very thin layers of copper side surface or the carrier side surface are exposed by the circuit that the resin bed is buried.
CN201410707733.9A 2013-11-29 2014-11-27 Surface treatment copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board Active CN104717831B (en)

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Families Citing this family (21)

* Cited by examiner, † Cited by third party
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JP6023367B1 (en) * 2015-06-17 2016-11-09 Ｊｘ金属株式会社 Copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method
JP6204430B2 (en) * 2015-09-24 2017-09-27 Ｊｘ金属株式会社 Metal foil, metal foil with release layer, laminate, printed wiring board, semiconductor package, electronic device and method for manufacturing printed wiring board
KR20170037750A (en) * 2015-09-25 2017-04-05 일진머티리얼즈 주식회사 Surface-treated Copper Foil and Method of manufacturing of the same
JP6294862B2 (en) * 2015-12-09 2018-03-14 古河電気工業株式会社 Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board
PH12017000015A1 (en) 2016-01-15 2018-08-06 Jx Nippon Mining & Metals Corp Copper foil, copper-clad laminate board, method for producing printed wiring board, method for poducing electronic apparatus, method for producing transmission channel, and method for producing antenna
KR20180047897A (en) * 2016-11-01 2018-05-10 케이씨에프테크놀로지스 주식회사 Electrodeposited copper foil with its surfaceprepared, process for producing the same and usethereof
WO2018110579A1 (en) * 2016-12-14 2018-06-21 古河電気工業株式会社 Surface treated copper foil and copper-clad laminate
JP7033905B2 (en) * 2017-02-07 2022-03-11 Ｊｘ金属株式会社 Manufacturing method of surface-treated copper foil, copper foil with carrier, laminate, printed wiring board and manufacturing method of electronic equipment
JP7002200B2 (en) * 2017-02-07 2022-01-20 Ｊｘ金属株式会社 Manufacturing method of surface-treated copper foil, copper foil with carrier, laminate, printed wiring board and manufacturing method of electronic equipment
WO2018181726A1 (en) * 2017-03-30 2018-10-04 古河電気工業株式会社 Surface-treated copper foil, and copper-clad laminate and printed wiring board using same
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JP7055049B2 (en) * 2017-03-31 2022-04-15 Ｊｘ金属株式会社 Surface-treated copper foil and laminated boards using it, copper foil with carriers, printed wiring boards, electronic devices, and methods for manufacturing printed wiring boards.
WO2018198905A1 (en) * 2017-04-25 2018-11-01 古河電気工業株式会社 Surface-treated copper foil
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US10581081B1 (en) * 2019-02-01 2020-03-03 Chang Chun Petrochemical Co., Ltd. Copper foil for negative electrode current collector of lithium ion secondary battery
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WO2022209990A1 (en) * 2021-03-29 2022-10-06 三井金属鉱業株式会社 Roughened copper foil, copper-clad laminate and printed wiring board
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CN113811093A (en) * 2021-08-09 2021-12-17 广州方邦电子股份有限公司 Metal foil, copper-clad laminated board, circuit board and preparation method of circuit board

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466517A (en) * 2000-09-22 2004-01-07 �źӵ�·ͭ����ʽ���� Copper foil for high-density ultrafine wiring board
CN1657279A (en) * 2004-02-06 2005-08-24 古河电路铜箔株式会社 Treated copper foil and circuit board
CN1217564C (en) * 2001-05-14 2005-08-31 日本电解株式会社 Roughened copper foil and making method thereof
CN1770953A (en) * 2004-10-06 2006-05-10 古河电路铜箔株式会社 Surface treated copper foil and circuit board
CN102203326A (en) * 2008-09-05 2011-09-28 古河电气工业株式会社 Ultrathin copper foil with carrier, and copper laminated board or printed wiring board

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3662404B2 (en) * 1997-11-19 2005-06-22 芝浦メカトロニクス株式会社 Wafer sheet stretching apparatus and pellet bonding apparatus using the same
TW499508B (en) * 1999-12-10 2002-08-21 Nippon Denkai Kk Roughening treated copper foil and producing method therefor
JP3622680B2 (en) * 2001-02-22 2005-02-23 住友金属工業株式会社 Ferritic stainless steel continuously annealed steel for mask frame of cathode ray tube and manufacturing method thereof
JP2002356789A (en) * 2001-05-30 2002-12-13 Nippon Mining & Metals Co Ltd Copper alloy foil for laminate
JP2003013156A (en) * 2001-07-04 2003-01-15 Nippon Mining & Metals Co Ltd Copper alloy foil for laminate
JP2004238647A (en) * 2003-02-04 2004-08-26 Furukawa Techno Research Kk Smoothened copper foil, and production method therefor
JP4172704B2 (en) * 2003-07-31 2008-10-29 日鉱金属株式会社 Surface-treated copper foil and substrate using the same
JP5129642B2 (en) * 2007-04-19 2013-01-30 三井金属鉱業株式会社 Surface treated copper foil, copper clad laminate obtained using the surface treated copper foil, and printed wiring board obtained using the copper clad laminate
JP5242710B2 (en) * 2010-01-22 2013-07-24 古河電気工業株式会社 Roughening copper foil, copper clad laminate and printed wiring board
JP5794806B2 (en) * 2011-03-30 2015-10-14 古河電気工業株式会社 Surface-treated copper foil, copper-clad laminate using the surface-treated copper foil, and printed wiring board
JP5871426B2 (en) * 2012-01-31 2016-03-01 古河電気工業株式会社 Surface treated copper foil for high frequency transmission, laminated plate for high frequency transmission and printed wiring board for high frequency transmission
JP5475897B1 (en) * 2012-05-11 2014-04-16 Ｊｘ日鉱日石金属株式会社 Surface-treated copper foil and laminate using the same, copper foil, printed wiring board, electronic device, and method for manufacturing printed wiring board
WO2013176133A1 (en) * 2012-05-21 2013-11-28 Jx日鉱日石金属株式会社 Printed wiring board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466517A (en) * 2000-09-22 2004-01-07 �źӵ�·ͭ����ʽ���� Copper foil for high-density ultrafine wiring board
CN1217564C (en) * 2001-05-14 2005-08-31 日本电解株式会社 Roughened copper foil and making method thereof
CN1657279A (en) * 2004-02-06 2005-08-24 古河电路铜箔株式会社 Treated copper foil and circuit board
CN1770953A (en) * 2004-10-06 2006-05-10 古河电路铜箔株式会社 Surface treated copper foil and circuit board
CN102203326A (en) * 2008-09-05 2011-09-28 古河电气工业株式会社 Ultrathin copper foil with carrier, and copper laminated board or printed wiring board

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