CN104943270B - The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board - Google Patents

The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board Download PDF

Info

Publication number
CN104943270B
CN104943270B CN201510147943.1A CN201510147943A CN104943270B CN 104943270 B CN104943270 B CN 104943270B CN 201510147943 A CN201510147943 A CN 201510147943A CN 104943270 B CN104943270 B CN 104943270B
Authority
CN
China
Prior art keywords
copper foil
layer
appendix body
copper
body according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510147943.1A
Other languages
Chinese (zh)
Other versions
CN104943270A (en
Inventor
宫本宣明
本多美里
石井雅史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Publication of CN104943270A publication Critical patent/CN104943270A/en
Application granted granted Critical
Publication of CN104943270B publication Critical patent/CN104943270B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses the manufacture method of the copper foil of appendix body, printed wiring board, layered product, e-machine and printed wiring board.Specifically, the present invention provides a kind of copper foil of the appendix body with good circuit formative.The copper foil of appendix body of the present invention sequentially possesses carrier, intermediate layer and very thin layers of copper, by the copper foil of appendix body using 30 DEG C/min be heated to 500 DEG C when produced amount of moisture as below 160ppm/g.

Description

Copper foil, printed wiring board, layered product, e-machine and the printed wiring board of appendix body Manufacture method
Technical field
The present invention relates to the system of a kind of copper foil of appendix body, printed wiring board, layered product, e-machine and printed wiring board Make method.
Background technology
Printed wiring board generally goes through following steps and manufactured：Insulated substrate is adhered to copper foil and copper clad laminate is made Afterwards, by being etched in copper-clad surface formation conductive pattern.With the miniaturization of e-machine in recent years, the increasing of high performance demand It is long, carry the high-density installation of part or the high frequency of signal is continued to develop, the micro- of conductive pattern is required to printed wiring board Refine (micro- spacing) or reply high frequency etc..
Corresponding to micro- spacing, the copper foil below 9 μm of thickness and then below 5 μm of thickness, but this very thin copper are required recently The mechanical strength of paper tinsel is low, easily ruptures when manufacturing printed wiring board or produces gauffer, so occurring in that the copper of following appendix body Paper tinsel：Metal foil with thickness is used as carrier, and very thin layers of copper is electrodeposited in metal foil across peel ply.By very thin copper After the surface of layer fits to insulated substrate and is thermally compressed, carrier is peeled off via peel ply and removed.By using resist Formed after circuit pattern, gone the etching of very thin layers of copper in the very thin layers of copper exposed using the etchant of Sulfuric-acid-hydrogen-peroxide system Method (the MSAP removed：Modified-Semi-Additive-Process, improves half additive process) and form fine circuits.
Here, for as the surface with the very thin layers of copper of the copper foil of the appendix body of the adhesive surface of resin, major requirement pole The peel strength of thin copper layer and resin base material is fully and after high-temperature heating, wet processed, welding, chemical treatments etc. Also it is sufficiently maintained its peel strength.As the method for improving the peel strength between very thin layers of copper and resin base material, generally Representational is the method for adhering in the very thin layers of copper of profile (concavo-convex, roughness) for increasing surface a large amount of roughening particles.
If however, used the conductor package substrate that fine circuit pattern is especially necessarily be formed in printed wiring board The big very thin layers of copper of this profile (concavo-convex, roughness), then can remain unwanted copper particle, generation circuit in circuit etch The problems such as defective insulation between pattern.
Therefore, in No. WO2004/005588 (patent document 1), as using conductor package substrate as the fine of representative The copper foil of the appendix body of circuit purposes, trial uses the copper of the appendix body of surface implementation roughening treatment not to very thin layers of copper Paper tinsel.The adaptation (peel strength) of this very thin layers of copper and resin without implementation roughening treatment is due to the low profile of very thin layers of copper The influence of (bumps, rugosity, roughness), and have the tendency of less than common printed wiring board-use copper-clad.Therefore, to appendix body Copper foil requirement is further to be improved.
Thus, in Japanese Patent Laid-Open 2007-007937 publications (patent document 2) and Japanese Patent Laid-Open 2010- In No. 006071 publication (patent document 3), the ultrathin copper foil and polyimides system resins substrate contact in appendix body is described The face of (bonding) set Ni layer and/or Ni alloy-layers, chromate coating is set, set Cr layers and/or Cr alloy-layers, Ni layers of setting and Chromate coating, Ni layers and Cr layers of setting.By setting these surface-treated layers, it can be roughened without roughening treatment or reduction The degree (miniaturization) of processing and make the ultrathin copper foil of polyimides system resins substrate and appendix body dhering strength obtain needed for Bonding strength.Also, also describe and be surface-treated using silane coupler, or implement antirust treatment.
[prior art literature]
[patent document]
[patent document 1] No. WO2004/005588 number；
[patent document 2] Japanese Patent Laid-Open 2007-007937 publications；
[patent document 3] Japanese Patent Laid-Open 2010-006071 publications.
The content of the invention
[the invention problem to be solved]
In the exploitation of the copper foil of appendix body, focus on ensures that the stripping of very thin layers of copper and resin base material is strong before this Degree.Accordingly, with respect to the circuit formative of very thin layers of copper, do not studied sufficiently also, still leave room for improvement.
Can carry out heating crimping when the copper foil of appendix body is fitted into resin from very thin layers of copper side, but now have due to The gases such as the vapor produced between carrier/very thin layers of copper and the situation for producing bubble (bulging (swelling)).If producing this Bulging is planted, then can produce the very thin layers of copper for forming circuit and be recessed, the problem of harmful effect is produced to circuit formative.This hair It is bright that a kind of copper foil of appendix body is provided, produced during by suppressing and the copper foil of appendix body is heated under given conditions The number of bulging, and with good etching.Or, the present invention provides a kind of copper foil of appendix body, by suppressing to appendix body The amount of moisture that produces when being heated under given conditions of copper foil, and suppress by resulting between carrier/very thin layers of copper The generation of bulging caused by the gases such as vapor, and with good etching.
[technological means for solving problem]
Based on above opinion complete the present invention be a kind of copper foil of appendix body in one aspect, sequentially possess carrier, in Interbed and very thin layers of copper, by the copper foil of the appendix body using 30 DEG C/min be heated to 500 DEG C when produced amount of moisture as Below 160ppm/g.
In one embodiment, the copper foil of the appendix body is heated with 30 DEG C/min for the copper foil of the appendix body of the present invention Produced amount of moisture is 0~130ppm/g during to 500 DEG C.
In another embodiment, the copper foil of the appendix body is added with 30 DEG C/min for the copper foil of the appendix body of the present invention Produced amount of moisture is 0~110ppm/g when heat is to 500 DEG C.
The present invention is a kind of copper foil of appendix body in another aspect, and it sequentially possesses carrier, intermediate layer and very thin layers of copper, By the copper foil of the appendix body using produced bulging during 220 DEG C of heating 4 hours as 20/dm2Below.
The copper foil of the appendix body of the present invention so that another embodiment in, by the copper foil of the appendix body with 220 DEG C plus Produced bulging is 0~15/dm when hot 4 hours2Below.
The copper foil of the appendix body of the present invention so that another embodiment in, by the copper foil of the appendix body with 400 DEG C plus Produced bulging is 0~60/dm when hot 10 minutes2Below.
The present invention appendix body copper foil so that another embodiment in, the intermediate layer contain selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition One or both of more than.
The present invention appendix body copper foil so that another embodiment in, the intermediate layer in the case of containing Cr, Contain 5 μ g/dm2The μ g/dm of the above 1002Following Cr, in the case of containing Mo, contains 50 μ g/dm2The μ g/dm of the above 10002With Under Mo, in the case of containing Ni, contain 100 μ g/dm2The μ g/dm of the above 400002Following Ni, in the case of containing Co, Contain 100 μ g/dm2The μ g/dm of the above 400002Following Co, in the case of containing Zn, contains 1 μ g/dm2The μ g/dm of the above 1202 Following Zn.
The present invention appendix body copper foil so that another embodiment in, the intermediate layer is with more than 25nm below 80nm Thickness contain organic matter.
The present invention appendix body copper foil so that another embodiment in, the organic matter is by being organised selected from nitrogenous The organic matter more than one or both of compound, organic compounds containing sulfur and carboxylic acid constituted.
The present invention appendix body copper foil so that another embodiment in, in the very thin layers of copper surface or the carrier Surface any surface or two sides have roughening treatment layer.
The present invention appendix body copper foil so that another embodiment in, the roughening treatment layer surface have choosing The layer of one or more of the group that free refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
The present invention appendix body copper foil so that another embodiment in, the antirust coat and the refractory layer are at least One layer contains the element selected from one or more of nickel, cobalt, copper, zinc.
The present invention appendix body copper foil so that another embodiment in, the antirust coat and the refractory layer are at least One layer is made up of the element selected from one or more of nickel, cobalt, copper, zinc.
The present invention appendix body copper foil so that another embodiment in, the roughening treatment layer on have it is described resistance to Thermosphere.
The present invention appendix body copper foil so that another embodiment in, the roughening treatment layer or the refractory layer It is upper that there is the antirust coat.
The present invention appendix body copper foil so that another embodiment in, on the antirust coat have the chromate Process layer.
The copper foil of the appendix body of the present invention so that another embodiment in, have on the chromating layer described Silane coupled process layer.
The present invention appendix body copper foil so that another embodiment in, the surface of the very thin layers of copper have be selected from The layer of one or more of the group being made up of refractory layer, antirust coat, chromating layer and silane coupled process layer.
The present invention appendix body copper foil so that another embodiment in, possess resin bed in the very thin layers of copper.
The present invention appendix body copper foil so that another embodiment in, the roughening treatment layer on possess resin Layer.
The present invention appendix body copper foil so that another embodiment in, selected from by the refractory layer, antirust coat, chromium Possesses resin bed on the layer of one or more of the group of hydrochlorate process layer and silane coupled process layer composition.
The present invention appendix body copper foil so that another embodiment in, the resin bed contains dielectric medium.
The present invention so that another aspect in be a kind of printed wiring board, using the present invention appendix body copper foil it is made Make.
The present invention so that another aspect in be a kind of e-machine, using the present invention printed wiring board manufactured by.
The present invention so that another aspect in be a kind of layered product, using the present invention appendix body copper foil manufactured by.
The present invention so that another aspect in be a kind of layered product, containing the present invention appendix body copper foil and resin, institute Part or all for stating the end face of the copper foil of appendix body is covered by the resin.
The present invention so that another aspect in be a kind of layered product, by the copper foil of a piece of appendix body of the invention from it is described carry Side or the very thin layers of copper side are laminated to the carrier side or the very thin copper of the copper foil of another appendix body of the invention Layer side is formed.
The layered product of the present invention is by the carrier side surface of the copper foil of a piece of appendix body in one embodiment Or the carrier side surface or the very thin layers of copper side of the copper foil of the very thin layers of copper side surface and another appendix body Surface is constituted via adhesive contact laminating as needed.
The present invention layered product in another embodiment, the carrier side surface of the copper foil of a piece of appendix body or The carrier of the copper foil of the very thin layers of copper side surface and another appendix body or the pole thin copper layer Even connect.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, use the present invention layered product.
The present invention so that another aspect in be a kind of layered product, part or all of its end face is covered by resin.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, comprise the following steps：In this hair Bright layered product is at least provided with this two layers of 1 resin bed and circuit；And at least form 1 resin bed and circuit this two layers Afterwards, the copper foil from the appendix body of the layered product peels off the very thin layers of copper.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, comprise the following steps：Prepare this The copper foil and insulated substrate of the appendix body of invention；The copper foil and insulated substrate of the appendix body are laminated；And will be described attached After the copper foil and insulated substrate of carrier are laminated, through the copper foil for stripping the appendix body foil carriers the step of and formed Copper clad laminate, is formed thereafter by any of semi-additive process, subtractive process, part addition process or improvement semi-additive process method Circuit.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, comprise the following steps：In this hair The very thin layers of copper side of the copper foil of bright appendix body or the carrier side circuit forming surface；In the way of burying the circuit Resin bed is formed in the very thin layers of copper side of the copper foil of the appendix body or the carrier side surface；The shape on the resin bed Into circuit；Formed on the resin bed after circuit, peel off the carrier or the very thin layers of copper；And peel off the carrier or institute State after very thin layers of copper, make to be formed in the very thin layers of copper side surface or described by removing the very thin layers of copper or the carrier The circuit being buried in the resin bed of carrier side surface exposes.
The present invention printed wiring board manufacture method in one embodiment, it is described on the resin layer formed circuit step Suddenly it is to be fitted in the copper foil of other appendix body on the resin bed from very thin layers of copper side or carrier side, it is described using being fitted in The copper foil of appendix body on resin bed and the step of form the circuit.
The manufacture method of the printed wiring board of the present invention is in another embodiment, described to fit on the resin layer in addition Appendix body copper foil be the present invention appendix body copper foil.
The present invention printed wiring board manufacture method so that another embodiment in, it is described on the resin layer formed electricity The step of road, is carried out by any of semi-additive process, subtractive process, part addition process or improvement semi-additive process method.
The present invention printed wiring board manufacture method so that another embodiment in, it is described will be in circuit forming surface Appendix body copper foil the appendix body copper foil the surface of carrier side or the surface of very thin layers of copper side there is substrate.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, comprise the following steps：This is sent out The very thin layers of copper side surface of the copper foil of bright appendix body or the carrier side surface and resin substrate are laminated；Described Appendix body copper foil and with very thin layers of copper side surface or the carrier side surface that the side that resin substrate is laminated is opposite side At least provided with this two layers of 1 resin bed and circuit；And after this two layers of 1 resin bed and circuit is at least formed, from described The copper foil of appendix body peels off the carrier or the very thin layers of copper.
The present invention so that another aspect in be a kind of manufacture method of printed wiring board, comprise the following steps：This is sent out The carrier side surface of the copper foil of bright appendix body and resin substrate are laminated；The copper foil of the appendix body and with tree The side of aliphatic radical flaggy pressure for opposite side very thin layers of copper side surface at least provided with this two layers of 1 resin bed and circuit；And at least Formed after this two layers of 1 resin bed and circuit, the carrier is peeled off from the copper foil of the appendix body.
[The effect of invention]
According to the present invention it is possible to provide a kind of copper foil of the good appendix body of circuit formative.
Brief description of the drawings
A~C is arriving for the concrete example of the manufacture method of the printed wiring board of the copper foil of the appendix body using the present invention in Fig. 1 The schematic diagram of wiring plate section in the step of untill plating circuit, removal plating resist application.
In Fig. 2 D~F be using the present invention appendix body copper foil printed wiring board manufacture method concrete example from The schematic diagram of wiring plate section in the step of copper foil of laminated resin and the 2nd layer of appendix body is untill laser beam drilling.
In Fig. 3 G~I be using the present invention appendix body copper foil printed wiring board manufacture method concrete example from Form the schematic diagram of wiring plate section in the step of through hole filler (via-fill) is untill the 1st layer of carrier is peeled off.
In Fig. 4 J~K be using the present invention appendix body copper foil printed wiring board manufacture method concrete example from The schematic diagram of wiring plate section in the step of fast-etching is untill projection copper post is formed.
Fig. 5 is the schematic diagram of the cross section of the width of the circuit pattern in embodiment and the etching using the schematic diagram The outline of the computational methods of coefficient (EF).
Embodiment
The copper foil ＞ of ＜ appendix bodies
The copper foil of the appendix body of the present invention sequentially possesses carrier, intermediate layer and very thin layers of copper.The copper foil of appendix body is in itself Application method is dealer it is well known that the surface of very thin layers of copper can be for example fitted in paper base material phenol resin, paper base material ring Oxygen tree fat, synthetic fibers cloth base material epoxy resin, glass cloth/paper composite base material epoxy resin, glass cloth/glass non-woven fabric are combined Base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystalline polymer film, fluororesin film etc. are absolutely Edge substrate simultaneously peels off carrier after being thermally compressed, and the very thin layers of copper for being bonded in insulated substrate is etched into the conductive pattern of target, Final manufacture printed wiring board.
＜ carriers ＞
Can be used for the present invention carrier typical case for be metal foil or resin film, such as with copper foil, copper alloy foil, nickel Paper tinsel, nickel alloy foil, iron foil, ferroalloy paper tinsel, stainless steel foil, aluminium foil, alloy foil, insulating resin film, polyimide film, LCD films Form provide.
There is provided for the carrier typical case that can be used for the present invention with the form of rolled copper foil or electrolytic copper foil.Generally, it is electrolysed Copper foil is copper is precipitate on the rotating cylinder of titanium or stainless steel and is manufactured from copper sulfate bath electrolysis, and rolled copper foil is that profit is repeated Manufactured with the plastic working and heat treatment of stack.As the material of copper foil, except refined copper, (JIS H3100 alloys are numbered C1100) or beyond the high-purity copper such as oxygen-free copper (JIS H3100 alloy numbering C1020 or JIS H3510 alloys numbering C1011), Such as can also use mix Sn copper, mix Ag copper, with the addition of Cr, Zr or Mg copper alloy, with the addition of Ni and Si etc. gloomy system of section The copper alloy of the class of copper alloy.
In addition, being used as electrolytic copper foil, it is possible to use following electrolyte composition and manufacturing condition make.
The situation of electrolytic copper foil is manufactured in following condition, TD (the manufacturing equipment neutralizations of copper foil of copper foil surface can be obtained The rectangular direction (width) of the direct of travel of copper foil) the electrolytic copper foil that Rz is small, TD 60 degree of glossiness are high.
＜ electrolyte constitutes ＞
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 can use the amines of below formula.
As long as in addition, the remainder for treatment fluid used in electrolysis, surface treatment or plating of the invention etc. does not have Have and especially express, be then water.
(in the chemical formula, R1And R2Selected from by hydroxy alkyl, ether, aryl, aromatic series substitution alkyl, unsaturated hydrocarbons The group of base, alkyl composition)
＜ manufacturing conditions ＞
Current density：70~100A/dm2
Electrolyte temperature：50~60 DEG C
Electrolyte linear velocity：3~5m/sec
Electrolysis time：0.5~10 minute
In addition, when term " copper foil " is used alone in this specification, also including copper alloy foil.
As long as the thickness of the carrier on can be used for the present invention is it is not also specifically limited, appropriate be adjusted to playing conduct The appropriate thickness of the aspect of the effect of carrier just can, can for example be set to more than 5 μm.But if blocked up, then production cost is carried Height, it is generally preferred that being set to less than 35 μm.Therefore, be 8~70 μm for the thickness typical case of carrier, it is more typical for for 12~ 70 μm, it is more typical for be 18~35 μm.In addition, for the viewpoint of reduction cost of material, the thickness of preferred vector is small.Cause This, is less than more than 5 μm 35 μm for the thickness of carrier typical case, preferably less than more than 5 μm 18 μm, preferably more than 5 μm 12 μm with Under, preferably less than more than 5 μm 11 μm, preferably less than more than 5 μm 10 μm.In addition, in the case where carrier thickness is small, it is logical in carrier Easily gauffer is produced during paper tinsel.In order to prevent gauffer, effectively for example make the transport roller of the copper foil manufacture device of appendix body Smoothly or shorten the distance of transport roller and next transport roller.In addition, in one embedment of the manufacture method as printed wiring board In the case of copper foil of the method (Enbedded Process) using appendix body, the rigidity of carrier is necessary for high.Therefore, for burying In the case of entering method, the thickness of carrier is preferably less than more than 18 μm 300 μm, preferably less than more than 25 μm 150 μm, is preferably Less than more than 35 μm 100 μm, be even more preferably less than more than 35 μm 70 μm.
Alternatively, it is also possible to set roughening treatment on carrier and the very thin layers of copper side of setting surface for the surface of opposite side Layer.It can use known method that roughening treatment layer is set, can also be set using following roughening treatments.Carrier and set Put the surface of very thin layers of copper side sets roughening treatment layer to have following advantage for the surface of opposite side：Carrier is had slightly from this When the face side for changing process layer is laminated to the supporters such as resin substrate, carrier and resin substrate are not easily stripped.
＜ intermediate layers ＞
Intermediate layer is set on the single or double of carrier.Other layers can also be set between carrier and intermediate layer.This Intermediate layer used in invention is constituted as follows：The step of copper foil of appendix body is laminated to insulated substrate before, make very thin Layers of copper is difficult to peel off from carrier, on the other hand, after the step of being laminated to insulated substrate, very thin layers of copper is peeled off from carrier. For example, the present invention appendix body copper foil intermediate layer can contain be selected from by Ni and Cr, Co, Fe, Mo, Ti, W, P, Cu, It is more than one or both of Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition. In addition, intermediate layer can be multilayer.
In addition, intermediate layer be sequentially laminated preferably on carrier nickel or nickel-containing alloys any layer and containing chromium, evanohm, The layer of more than one in the oxide of chromium and constitute.Moreover, any layer of nickel or nickel-containing alloys and/or containing chromium, evanohm, Zinc is preferably comprised in the layer of one or more of the oxide of chromium.Here, nickel-containing alloys refer to by nickel and selected from by cobalt, iron, chromium, The alloy that the element of one or more of the group that molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium are constituted is constituted.Nickel-containing alloys It can be the alloy being made up of more than 3 kinds of element.In addition, evanohm refer to by chromium and selected from by cobalt, iron, nickel, molybdenum, zinc, tantalum, The alloy that the element of one or more of the group that copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium are constituted is constituted.Evanohm be alternatively by 3 kinds with On element constitute alloy.In addition, the layer containing one or more of chromium, evanohm, the oxide of chromium can also be chromate Process layer.Here, chromating layer refers to by the layer containing chromate or the liquid handling of bichromate.Chromic acid salt treatment Layer can also contain the metals such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium.In the present invention, chromium will be passed through Acid anhydrides or the chromating layer of potassium dichromate aqueous solution processing are referred to as pure chromating layer., will be through in addition, in the present invention The chromating layer for crossing the processing of the treatment fluid containing acid anhydrides or potassium bichromate and zinc is referred to as zinc chromate process layer.
In addition, intermediate layer is sequentially laminated appointing in nickel, nickel-zinc alloy, nickel-phosphor alloy, nickel-cobalt alloy preferably on carrier A kind of any of layer and zinc chromate process layer, pure chromating layer, chrome plating layer and constitute, intermediate layer is further excellent It is selected on carrier and is sequentially laminated nickel dam or nickel-zinc alloy-layer and zinc chromate process layer and constitutes, or is sequentially laminated nickel-zinc alloy Layer and pure chromating layer or zinc chromate process layer and constitute.Because the bonding force of nickel and copper is higher than the bonding of chromium and copper Power, so when peeling off very thin layers of copper, as the stripping on the interface of very thin layers of copper and chromating layer.In addition, in the middle of expecting The nickel of layer prevents the copper component to be diffused into the barriering effect of very thin layers of copper from carrier.Additionally, it is preferred that forming chromate in intermediate layer Process layer rather than chrome plating.Chrome plating is forming very thin because forming the chromium oxide layer of densification on surface using plating Resistance rises and easily produces pin hole during copper foil.The surface of chromating layer is formd because being formed be not as fine and close as chrome plating Chromium oxide layer, so being difficult to turn into resistance when forming ultrathin copper foil using plating, it is possible to reduce pin hole.Here, shape is passed through Into zinc chromate process layer as chromating layer, resistance when forming ultrathin copper foil using plating gets lower than common chromium Hydrochlorate process layer, can further suppress the generation of pin hole.
In the case where using electrolytic copper foil as carrier, for the viewpoint for reducing pin hole, in preferably being set in bright face Interbed.
Chromating layer in intermediate layer is present in the interface of very thin layers of copper from can obtain following characteristic side compared with unfertile land It is preferred for face：Very thin layers of copper will not be peeled off from carrier the step of being laminated to insulated substrate before, on the other hand, be laminated to Very thin layers of copper can be peeled off after the step of insulated substrate from carrier.Be not provided with nickel dam or nickeliferous alloy-layer (for example nickel-zinc is closed Layer gold) and in the case of making the border that chromating layer is present in carrier and very thin layers of copper, fissility is hardly improved, There is no chromating layer and by the feelings of nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) and very thin layers of copper contact laminating Under condition, according to the nickel amount in nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy-layer), peel strength is too strong or excessively weak, it is impossible to Obtain appropriate peel strength.
In addition, if chromating layer is present in carrier and nickel dam or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) Border, then peel off very thin layers of copper when intermediate layer also can with stripping, that is to say, that can be produced between carrier and intermediate layer Peel off, thus it is not preferred.This situation can not only be produced when in the case where setting chromating layer with the interface of carrier, i.e., Make the interface with very thin layers of copper that chromating layer is set, if chromium content is excessive, may also produce.Think that its reason is： Due to the easy solid solution of copper and mickel, if so they contact, can improve bonding force because of phase counterdiffusion, be not easily stripped, On the other hand, because chromium and copper are difficult solid solution, phase counterdiffusion is not likely to produce, so at the interface of chromium and copper, bonding force is weak, easily Peel off.In addition, in the case where the nickel amount in intermediate layer is not enough, because only existing micro chromium between carrier and very thin layers of copper, So both are closely sealed and are not easily stripped.
The nickel dam in intermediate layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) can for example utilize plating, electroless plating And the wet type plating of class or the dry type plating of class of sputter, CVD and PDV of dipping plating are formed.For the viewpoint of cost It is preferred that electroplating.In addition, in the case where carrier is resin film, it is possible to use the dry type plating of CVD and PDV class or electroless plating The wet type plating formation intermediate layer of deposited and dipping plating class.
In addition, chromating layer is formed such as can utilize electrolytic chromate or dipping chromate, but utilize electrolysis Chromate formation makes very thin layers of copper become good from the peel strength of carrier due to that can improve chromium concn, it is advantageous to.
Additionally, it is preferred that the adhesion amount of nickel is 100~40000 μ g/dm in the intermediate layer2, the adhesion amount of chromium is 5~100 μ g/ dm2, the adhesion amount of zinc is 1~70 μ g/dm2.By controlling the adhesion amount of nickel, chromium, zinc like this, the copper of appendix body of the invention Paper tinsel can control to peel off the Ni amounts on the surface of the very thin layers of copper after very thin layers of copper from the copper foil of appendix body.In order to so control to peel off The Ni amounts on very thin layers of copper surface afterwards, preferably reduce the Ni adhesion amounts in intermediate layer, and intermediate layer is contained suppression Ni to very thin The metal species (Cr, Zn) of layers of copper side diffusion.For this viewpoint, the Ni contents in intermediate layer are preferably 100~40000 μ g/ dm2, more preferably 200 μ g/dm2The μ g/dm of the above 200002Hereinafter, more preferably 500 μ g/dm2The μ g/ of the above 10000 dm2Hereinafter, more preferably 700 μ g/dm2The μ g/dm of the above 50002Below.In addition, Cr preferably comprises 5~100 μ g/dm2, enter One step is preferably 8 μ g/dm2The μ g/dm of the above 502Hereinafter, more preferably 10 μ g/dm2The μ g/dm of the above 402Hereinafter, further Preferably 12 μ g/dm2The μ g/dm of the above 302Below.Zn preferably comprises 1~70 μ g/dm2, more preferably 3 μ g/dm2The above 30 μg/dm2Hereinafter, more preferably 5 μ g/dm2The μ g/dm of the above 202Below.If controlling the copper foil stripping from appendix body very thin (such as Ni amounts are 5~300 μ g/dm to the Ni amounts on the very thin layers of copper surface after layers of copper2), then there is the etching of very thin layers of copper (readily soluble Solution property or circuitry shapes etc.) improve and other effects.Alternatively, it is also possible to replace described nickel using cobalt.Now the adhesion amount of cobalt can be with It is set to identical with the adhesion amount of nickel.
The intermediate layer of the copper foil of the appendix body of the present invention can sequentially be laminated nickel dam and containing nitrogenous organic compound on carrier Any organic matter layer in thing, organic compounds containing sulfur and carboxylic acid and constitute, in intermediate layer the adhesion amount of nickel be 100~ 40000μg/dm2.In addition, the intermediate layer of the copper foil of the appendix body of the present invention also can be sequentially laminated containing nitrogenous organic on carrier Any organic matter layer and nickel dam in compound, organic compounds containing sulfur and carboxylic acid and constitute, the adhesion amount of nickel in intermediate layer For 100~40000 μ g/dm2.As described above, in the copper foil of the appendix body of the present invention, very thin layers of copper is peeled off from the copper foil of appendix body The Ni on very thin layers of copper surface measures control afterwards, in order to control the Ni amounts on the very thin layers of copper surface after peeling off like this, preferably subtracts Lack the Ni adhesion amounts in intermediate layer, and intermediate layer is contained suppression Ni and contain nitrogenous organic compound to what very thin layers of copper side was spread Any organic matter layer in thing, organic compounds containing sulfur and carboxylic acid.For this viewpoint, the Ni contents in intermediate layer are preferably 100~40000 μ g/dm2, more preferably 200 μ g/dm2The μ g/dm of the above 200002Hereinafter, more preferably 300 μ g/ dm2The μ g/dm of the above 100002Hereinafter, more preferably 500 μ g/dm2The μ g/dm of the above 50002Below.Alternatively, it is also possible to use Cobalt replaces the nickel.Now the adhesion amount of cobalt can be set to identical with the adhesion amount of nickel.In addition, conduct should organise containing nitrogenous Any organic matter in compound, organic compounds containing sulfur and carboxylic acid, can enumerate BTA (BTA), MBT (sulfydryl benzos Thiazole) etc..
In addition, as the organic matter contained by intermediate layer, preferably using by being organised selected from organic compounds containing nitrogen, sulfur-bearing The organic matter more than one or both of compound and carboxylic acid constituted.Organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid In, organic compounds containing nitrogen includes the organic compounds containing nitrogen with substituent.As specific organic compounds containing nitrogen, preferably Use the l, 2,3 triazole, carboxyl benzotriazole, N ' as the triazole compounds with substituent, N '-bis- (BTAs Ylmethyl) 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- benzene And imidazole mercaptan etc..
As carboxylic acid, particularly preferably using monocarboxylic acid, wherein preferably using oleic acid, linolenic acid and linolenic acid etc..
The organic matter preferably contains more than 25nm below 80nm with thickness gauge, further preferably more than 30nm 70nm with Under.Intermediate layer can also contain a variety of (more than one) described organic matter.
In addition, the thickness of organic matter can utilize in the following manner measurement.
The organic matter thickness G T.GT.GT in ＜ intermediate layers
By the very thin layers of copper of the copper foil of appendix body after carrier stripping, to the surface for the intermediate layer side of very thin layers of copper exposed XPS measuring is carried out with the surface of the intermediate layer side of the carrier exposed, depth profile (depth profile) is made.And it is possible to By from the surface of the intermediate layer side of very thin layers of copper concentration of carbon be set to A (nm) as below 3at% depth at first, will be from carrier The surface of intermediate layer side play concentration of carbon and be set to B (nm) as below 3at% depth at first, A and B sum total is set to middle The thickness (nm) of the organic matter of layer.
XPS operating condition is as follows.
Device：XPS measuring device (ULVAC-PHI companies, model 5600MC)
Final vacuum：3.8×10-7Pa
X-ray：Monochrome is AlK α or polyenergetic is MgK α, and X-ray is output as 300W, and area of detection is 800 μm of φ, examination The angle that sample and detector are formed is 45 °
Ion beam：Ionic species is Ar+, accelerating potential is 3kV, and scan area is 3mm × 3mm, and sputtering rate is 2.8nm/min is (with SiO2Conversion)
On the application method of the organic matter contained by intermediate layer, below, simultaneously also to forming intermediate layer in carrier foils Method carry out narration one side illustrate.The organic matter can be dissolved in solvent and the impregnated carrier in the solvent, Or intermediate layer is formed at load to the face in intermediate layer will be formed using spray, spray-on process, method of dripping and electrodeposition process etc. On body, not especially using the necessity of the method limited.Now the concentration of organic system agent is complete in the organic matter in solvent The scope that preferred concentration is 0.01g/L~30g/L in portion, liquid temperature is 20~60 DEG C.The concentration of organic matter is not particularly limited, Concentration is not high or low original problematic.In addition, the concentration of organic matter is higher, carrier and the dissolving organic matter in addition solvent Time of contact it is longer, then the organic matter thickness for having the tendency of intermediate layer more increases.Also, the organic matter thickness in intermediate layer is thick In the case of, there is the effect increase for suppressing the organic matter that Ni spreads to very thin layers of copper side.
In addition, intermediate layer is sequentially laminated nickel and molybdenum or cobalt or molybdenum-cobalt alloy and constituted preferably on carrier.Due to nickel and copper Bonding force of the bonding force higher than molybdenum or cobalt and copper, so when peeling off very thin layers of copper, can in very thin layers of copper and molybdenum or cobalt or The interface peel of molybdenum-cobalt alloy.In addition, expecting the barrier that copper component spreads from from carrier to very thin layers of copper of preventing of the nickel in intermediate layer Effect.
In addition, the nickel can also be nickeliferous alloy.Here, nickeliferous alloy refer to by nickel and selected from by cobalt, iron, The alloy that the element of one or more of the group that chromium, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium are constituted is constituted.In addition, institute It can also be the alloy containing molybdenum to state molybdenum.Here, the alloy containing molybdenum refer to by molybdenum and selected from by cobalt, iron, chromium, nickel, zinc, tantalum, copper, The alloy that the element of one or more of the group that aluminium, phosphorus, tungsten, tin, arsenic and titanium are constituted is constituted.In addition, the cobalt can also be Alloy containing cobalt.Here, the alloy containing cobalt refers to by cobalt and selected from by molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic And the alloy that the element of one or more of the group of titanium composition is constituted.
Molybdenum-cobalt alloy can also containing the element beyond molybdenum, cobalt (be selected from by cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium, The element of one or more of the group that phosphorus, tungsten, tin, arsenic and titanium are constituted).
In the case where using electrolytic copper foil as carrier, for the viewpoint for reducing pin hole, in preferably being set in bright face Interbed.
Molybdenum or cobalt or molybdenum-cobalt alloy layer in intermediate layer are present in the interface of very thin layers of copper from obtaining following characteristic compared with unfertile land It is preferred for aspect：The step of being laminated to insulated substrate before, very thin layers of copper will not be peeled off from carrier, on the other hand, in layer Very thin layers of copper can be peeled off after the step of being pressed onto insulated substrate from carrier.Make molybdenum or cobalt or molybdenum-cobalt alloy being not provided with nickel dam In the case that layer is present in the border of carrier and very thin layers of copper, the situation for thering is fissility hardly to improve, in no molybdenum or cobalt Or molybdenum-cobalt alloy layer and by nickel dam and very thin layers of copper contact laminating in the case of, the nickel amount in good grounds nickel dam, peel strength mistake It is strong or excessively weak and the situation of appropriate peel strength can not be obtained.
In addition, if molybdenum or cobalt or molybdenum-cobalt alloy layer are present in the border of carrier and nickel dam, then when having the very thin layers of copper of stripping Intermediate layer also with stripping situation, that is to say, that have can be peeling between carrier and intermediate layer thus undesirable situation. This situation can not only be produced when in the case where setting molybdenum or cobalt or molybdenum-cobalt alloy layer with the interface of carrier, though with it is very thin The interface of layers of copper sets molybdenum or cobalt or molybdenum-cobalt alloy layer, if molybdenum amount or cobalt amount are excessive, may also produce.Think its reason It is：Due to the easy solid solution of copper and mickel, if so their contacts, can improve bonding force because of phase counterdiffusion, be difficult Peel off, on the other hand, because molybdenum or cobalt and copper are difficult solid solution, phase counterdiffusion is not likely to produce, so in molybdenum or cobalt or molybdenum-cobalt alloy On the interface of layer and copper, bonding force is weak, is easily peeled off.In addition, in the case where the nickel amount in intermediate layer is not enough, having because in carrier Micro molybdenum or cobalt is only existed between very thin layers of copper, so both situations that are closely sealed and being not easily stripped.
The nickel and cobalt or molybdenum-cobalt alloy in intermediate layer can for example utilize the wet of the class of plating, electroless plating and dipping plating The dry type plating of the class of formula plating or sputter, CVD and PDV is formed.In addition, molybdenum can only utilize the dry of CVD and PDV class Formula plating is formed.Preferably electroplated for the viewpoint of cost.
In intermediate layer, preferably the adhesion amount of nickel is 100~40000 μ g/dm2, the adhesion amount of molybdenum is 10~1000 μ g/dm2, The adhesion amount of cobalt is 10~1000 μ g/dm2.As described above, the copper foil control of the appendix body of the present invention is shelled from the copper foil of appendix body It is excellent in order to control the Ni amounts on the very thin layers of copper surface after peeling off like this from the Ni amounts on the surface of very thin layers of copper after very thin layers of copper Choosing reduce intermediate layer Ni adhesion amounts, and make intermediate layer contain suppress Ni spread to very thin layers of copper side metal species (Co, Mo).For this viewpoint, nickel adhesion amount is preferably set to 100~40000 μ g/dm2, it is preferably set to 200~20000 μ g/dm2, More preferably it is set to 300~15000 μ g/dm2, more preferably it is set to 300~10000 μ g/dm2.In the case of containing molybdenum in intermediate layer, Molybdenum adhesion amount is preferably set to 10~1000 μ g/dm2, molybdenum adhesion amount is preferably set to 20~600 μ g/dm2, more preferably it is set to 30~400 μg/dm2.In the case of containing cobalt in intermediate layer, cobalt adhesion amount is preferably set to 10~1000 μ g/dm2, cobalt adhesion amount is preferably set to 20~600 μ g/dm2, more preferably it is set to 30~400 μ g/dm2。
In addition, as described above, in the case that intermediate layer is sequentially laminated nickel and molybdenum or cobalt or molybdenum-cobalt alloy on carrier, such as Fruit reduction is used for setting the current density in the plating processing of molybdenum or cobalt or molybdenum-cobalt alloy layer, slows down the travelling speed of carrier, then The density for having the tendency of molybdenum or cobalt or molybdenum-cobalt alloy layer is improved.If the density of the layer containing molybdenum and/or cobalt is improved, nickel dam Nickel be difficult diffusion, can control peel off after very thin layers of copper surface Ni amounts.
In the case where one side sets intermediate layer, the antirust coats such as Ni coating preferably only are being set in the opposing face of carrier.Separately Outside, in the case where setting intermediate layer using chromic acid salt treatment or zinc chromate processing or plating processing, it is believed that have chromium or zinc etc. A part for the metal of attachment becomes the situation of hydrate or oxide.
The copper foil of the appendix body of the present invention is produced when being controlled as being heated to 500 DEG C with 30 DEG C/min in one aspect Amount of moisture turn into below 160ppm/g.If heating the copper foil of appendix body, have because being produced between carrier/very thin layers of copper The gas such as vapor and produce the situation of bubble (bulging).If producing this bulging, it can produce for forming circuit Very thin layers of copper depression, the problem of being had undesirable effect to circuit formative.On the other hand, by using inhibiting spy as described above The copper foil of the appendix body of the generation of moisture, can suppress the generation of bulging, the circuit shape of very thin layers of copper well after fixed heat treatment The change that becomes second nature is good.Produced amount of moisture when the copper foil of appendix body is heated into 500 DEG C with 30 DEG C/min if it exceeds 160ppm/g, the then number bloated between carrier/very thin layers of copper turns into 30/dm2More than, it is difficult to etch very thin layers of copper and form ratio L/S=30 μm/30 μm finer wirings, such as L/S=25 μm/25 μm of fine wiring, such as L/S=20 μm/20 μm Fine wiring, such as L/S=15 μm/15 μm of fine wiring.
The copper foil of the appendix body of present invention amount of moisture produced when being preferably controlled to be heated to 500 DEG C with 30 DEG C/min As 0~130ppm/g, more preferably control is 0~110ppm/g, and even more preferably control is 0~90ppm/g, further more It is preferably controlled to 0~70ppm/g.
The copper foil control of appendix body is to be heated 4 hours with 220 DEG C in another aspect by the copper foil of the appendix body of the present invention When produced bulging turn into 20/dm2Below.If heating the copper foil of appendix body, have because between carrier/very thin layers of copper The gases such as produced vapor and the situation for producing bubble (bulging).If producing this bulging, it can produce for being formed The very thin layers of copper depression of circuit, the problem of being had undesirable effect to circuit formative.On the other hand, the copper of appendix body of the invention Paper tinsel suppresses the generation of bulging well, and the circuit formative of very thin layers of copper becomes good.If the copper foil of appendix body added with 220 DEG C Produced bulging is more than 20/dm when hot 4 hours2, then it is difficult to etch very thin layers of copper and formed than L/S=30 μm/30 μm more Fine wiring, such as L/S=25 μm/25 μm of fine wiring, such as L/S=20 μm/20 μm of fine wiring, such as L/S =15 μm/15 μm of fine wiring.In addition, " being heated 4 hours with 220 DEG C " represents the copper foil of appendix body being fitted in insulation Substrate and the typical heating condition in the case of being thermally compressed.
The bulging produced when being preferably controlled to heat 4 hours with 220 DEG C of the copper foil of the appendix body of the present invention turns into 0~15 Individual/dm2Hereinafter, more preferably control is 0~12/dm2, even more preferably control is 0~9/dm2, even more preferably control It is made as 0~5/dm2。
In addition, the copper foil of the appendix body of the present invention is even more preferably controlled as further harsh heating condition 0~60/dm is turned into produced bulging during 400 DEG C of heating 10 minutes2Hereinafter, more preferably control is 0~50/dm2, Even more preferably control is 0~40/dm2, even more preferably control is 0~30/dm2。
It is attached that the number for being controlled or being bloated to make moisture yield during heating as described above is controlled The copper foil of carrier, it is important that control during manufacture as follows.
[plating condition for being used for being formed intermediate layer]
By the way that based on following plating condition formation intermediate layer, moisture yield when can make heating as described above is obtained The copper foil of the appendix body controlled to the number of control or bulging.
(1) pre-treatment
It is used as pre-treatment by carrying out degreasing and pickling, can effectively carries out follow-up plating processing.
(degreasing)
By degreasing, plated surface application is cleaned, surface wettability lifting, it is possible to effectively carry out follow-up pickling.
Basic handling：By carrier impregnation in sodium hydrate aqueous solution (1~100g/L).
Surfactant：If adding proper amount of surfactant in sodium hydrate aqueous solution, surface tension reduction, It is more effective and preferred.
Electrolytic degreasing：And if with following any electrolysis, degreasing can be more effectively carried out.
(a) there was only negative electrode degreasing (10A/dm2Left and right)
(b) there was only anode degreasing (5A/dm2Left and right)
(c) negative electrode degreasing → anode degreasing
(d) negative electrode degreasing → anode degreasing → negative electrode degreasing
(pickling)
By carrying out pickling after the degreasing, in the case where carrier is copper foil, the cupric oxide on surface etc. can be removed, Can expose the copper surface of activity.It therefore, it can effectively carry out follow-up nickel plating.
Basic handling：By carrier impregnation in sulfuric acid (50mL/L).
Oxidant：It is preferred that making in sulfuric acid containing oxidants such as persulfate, hydrogen peroxide., can by containing oxidant Expose the surface of activity slightly to cut down carrier surface.
(2) nickel plating or cobalt plating
After preceding processing, nickel plating or cobalt plating are then carried out.Now, it is important that be finish-machined to fine and close, uniform and no scarce Sunken coating.As nickel plating or cobalt plating, carried out in following condition.
Plating solution
Nickel or cobalt：20~200g/L
Boric acid：5~60g/L
Liquid temperature：40~65 DEG C
pH：1.5~5.0, preferably 2.0~3.0.By the way that pH to be set to obtain lower slightly periodically progress plating processing, and produce Raw hydrogen, makes cathode surface turn into reducing environment.It therefore, it can suppress the generation moisture such as oxide, hydroxide, hydrate The generation of reason key element.
Current density：0.5~20A/dm2, preferably 2~8A/dm2.Handled under low current density due to not being easily caused Plating is slightly crisp, as the few and fine and close coating of defect, it is advantageous to.
Stir (liquid internal circulating load)
100~1000L/ minutes.The gas release of the hydrogen of generation can be made to become good more than liquid internal circulating load, the defect such as pin hole becomes It is few.In addition, there is the effect for reducing thickness of diffusion layer, the generation of the reason for hydroxide etc. produces moisture key element can be suppressed.
Travelling speed
2~30m/ minutes, preferably 5~10m/ minutes.Travelling speed can form smooth and fine and close Ni layers slowly.
Additive
Additive is preferably used with polishing material next time and secondary polishing material.Thus, crystal is smoothened and densification.Cause This, the defect produced by plating is reduced, and the absorption of moisture is reduced.
(polishing material)
It is 1,5- naphthalene disulfonates：2~10g/L, 1,3,6- naphthalene trisulfonic acid sodium：10~30g/L, para toluene sulfonamide： 0.5~4g/L, saccharin sodium：Any of 0.5~5g/L.
(secondary polishing material)
It is formalin：0.5~5g/L, gelatin：0.005~0.5g/L, thiocarbamide：0.05~1.0g/L, propargyl alcohol： 0.01~0.3g/L, 1,4- butynediols：0.05~0.5g/L, cyanoethanol：Any of 0.05~0.5g/L.
After the metal-plateds such as nickel plating are carried out, (3) chromic acid salt treatment is then carried out under the following conditions or in following condition The lower processing for carrying out (4) using organic matter.
(3) chromic acid salt treatment
Treatment fluid
Chromium：0.5~6.0g/L
Zinc：0.1~2.0g/L
pH：2.5~5.0
Liquid temperature：25~60 DEG C
Current density：0.1~4A/dm2
In addition, other elements can also be contained in the treatment fluid of chromic acid salt treatment.
(4) processing of organic matter is utilized
Treatment fluid
Organic matter：0.1~20g/L
pH：2~5
Liquid temperature：20~40 DEG C
Dip time：5~30 seconds
Organic matter preferably the organic matter, for example comprising in organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid Any organic matter.
[forming the processing carried out behind intermediate layer untill very thin layers of copper is formed]
After intermediate layer is formed untill very thin layers of copper is formed, following heat and/or reduction is preferably further carried out Processing.By carrying out this processing, the copper for the appendix body that moisture yield when can make heating as described above is controlled Paper tinsel.
(5) heat
After the processing of chromic acid salt treatment or utilization organic matter, by being heated under the following conditions before copper facing And remove moisture removal.
For example, being heated 1 minute with 100~200 DEG C, preferably 180 DEG C or so using being handled on line.Also, if also simultaneously With using IR heaters heating, then more effectively.In addition, if being heated when being passed through hydrogen, then also there is reduction effect Really, further effectively.
(6) reduction treatment
By being post-processed under the following conditions using reducing agent, it is possible to reduce O (oxygen).
For example, carrying out impregnation process using the formic acid (0.1~100g/L) as reducing agent.
The very thin layers of copper ＞ of ＜
Very thin layers of copper is set on the intermediate layer.Other layers can also be set between intermediate layer and very thin layers of copper.Very thin copper Layer can be formed by using the plating of the electrobaths such as copper sulphate, cupric pyrophosphate, sulfamic acid copper, copper cyanider, from can profit For viewpoint with high current density formation layers of copper, the bath of preferably sulfuric acid copper.The thickness of very thin layers of copper is not particularly limited, generally It is thinner than carrier, for example, less than 12 μm.For typical case be 0.5~12 μm, it is more typical for be 1~5 μm, it is further more typical and Say as 1.5~5 μm, it is further typical for be 2~5 μm.In addition, very thin layers of copper can also be arranged on the two-sided of carrier.
The copper foil of appendix body of the invention can be used to make layered product (copper foil covered laminate etc.).It is used as the lamination Body, for example, can be the sequentially composition of lamination " very thin layers of copper/intermediate layer/carrier/resin or prepreg " or sequentially layer The composition of pressure " carrier/intermediate layer/very thin layers of copper/resin or prepreg " or sequentially lamination " very thin layers of copper/intermediate layer/ The composition of carrier/resin or prepreg/carrier/intermediate layer/very thin layers of copper " or sequentially lamination " carrier/intermediate layer/pole The composition of thin copper layer/resin or prepreg/very thin layers of copper/intermediate layer/carrier ".As long as the resin or the following trees of prepreg Lipid layer just can, resin, hardening of resin agent, compound, hardening accelerator, dielectric used in following resin beds can also be included Matter, catalysts, crosslinking agent, polymer, prepreg, framework material etc..In addition, the copper foil of appendix body can also be when overlooking Less than resin or prepreg.
＜ roughening treatments and other surface treatment ＞
Can be by any surface or two sides on the surface of very thin layers of copper or the surface of carrier for example in order that and insulation base The adaptation of plate well waits and implements roughening treatment, so as to set roughening treatment layer.Roughening treatment for example can be by using copper Or copper alloy forms roughening particle and carried out.Roughening treatment can also be fine.Roughening treatment layer can be by selected from by copper, nickel, The layer that any simple substance in the group that cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc are constituted or the alloy comprising any above are constituted Deng.In addition, after using copper or copper alloy formation roughening particle, can also further utilize nickel, cobalt, copper, the simple substance of zinc or conjunction Gold etc. is configured the roughening treatment of offspring or three particles.Thereafter, it is possible to use nickel, cobalt, copper, the simple substance or alloy of zinc Etc. refractory layer and/or antirust coat is formed, it also can further implement the processing such as chromic acid salt treatment, silane coupled processing on its surface. Or without roughening treatment nickel, cobalt, copper, the simple substance of zinc or alloy etc. can also be utilized to form refractory layer and/or antirust coat, Further implement the processing such as chromic acid salt treatment, silane coupled processing on its surface.That is, can roughening treatment layer table Face is formed selected from one or more of group being made up of refractory layer, antirust coat, chromating layer and silane coupled process layer Layer, can also very thin layers of copper surface formed be selected from by refractory layer, antirust coat, chromating layer and silane coupled processing The layer of one or more of the group that layer is constituted.In addition, the refractory layer, antirust coat, chromating layer, silane coupled processing Layer can form multilayer (such as more than 2 layers, 3 layers with first-class) respectively.
Here, chromating layer refers to utilize the liquid for including chromic anhybride, chromic acid, dichromic acid, chromate or bichromate Body carried out the layer of processing.Chromating layer can also containing cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and The elements such as titanium (can be any forms such as metal, alloy, oxide, nitride, sulfide).It is used as the tool of chromating layer Style, can enumerate and carry out the chromating layer of processing, using comprising chromic acid using chromic anhybride or potassium dichromate aqueous solution The treatment fluid of acid anhydride or potassium bichromate and zinc carried out chromating layer of processing etc..
As refractory layer, antirust coat, known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat Can include to be selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, the group of tantalum One or more of element layer or by selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, Metal level or alloy-layer that the element of one or more of gold, silver, platinum family element, iron, the group of tantalum is constituted.In addition, refractory layer And/or antirust coat can also contain comprising selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum Oxide, nitride, the silicide of the element of one or more of race's element, iron, the group of tantalum.In addition, refractory layer and/or antirust Layer can also be the layer for including nickel-zinc alloy.In addition, refractory layer and/or antirust coat can also be nickel-zinc alloy-layers.The nickel- Zinc alloy layer can contain nickel 50wt%~99wt%, zinc 50wt%~1wt% in addition to inevitable impurity.It is described The zinc of nickel-zinc alloy-layer and the total adhesion amount of nickel can be 5~1000mg/m2, preferably 10~500mg/m2, preferably 20~ 100mg/m2.In addition, the adhesion amount and the adhesion amount of zinc of the nickel of the layer comprising nickel-zinc alloy or the nickel-zinc alloy-layer Ratio (adhesion amount of adhesion amount/zinc of=nickel) preferably 1.5~10.In addition, the layer comprising nickel-zinc alloy or the nickel- The preferred 0.5mg/m of adhesion amount of the nickel of zinc alloy layer2~500mg/m2, more preferably 1mg/m2~50mg/m2.In refractory layer and/or In the case that antirust coat is the layer comprising nickel-zinc alloy, the adaptation lifting of copper foil and resin substrate.
For example, it is 1mg/m that refractory layer and/or antirust coat, which can be adhesion amounts,2~100mg/m2, preferably 5mg/m2~50mg/ m2Nickel or nickel alloy layer and adhesion amount be 1mg/m2~80mg/m2, preferably 5mg/m2~40mg/m2Tin layers be sequentially laminated and Into the nickel alloy layer can be made up of any of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt.In addition, refractory layer and/or antirust The total adhesion amount of layer preferably nickel or nickel alloy and tin is 2mg/m2~150mg/m2, more preferably 10mg/m2~70mg/m2.Separately Outside, refractory layer and/or antirust coat preferably [the nickel adhesion amount in nickel or nickel alloy]/[tin adhesion amount]=0.25~10, more preferably 0.33~3.If using the refractory layer and/or antirust coat, the copper foil of appendix body is processed into after printed wiring board, circuit Peel strength, chemical-resistant deterioration rate of the peel strength etc. become good.
In addition, for setting the silane coupler of silane coupled process layer to use known silane coupler, such as Amino system silane coupler or epoxy silane coupler, sulfydryl system silane coupler can be used.In addition, silane coupler can To use vinyltrimethoxy silane, ethenylphenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy Silane, γ-glycidoxypropyltrimewasxysilane, 4- glycidyls butyl trimethoxy silane, gamma-amino propyl group Triethoxysilane, N- β (amino-ethyl) gamma-aminos propyl trimethoxy silicane, N-3- (4- (3- amino propoxyl group) fourth oxygen Base) propyl group -3- TSL 8330s, imidizole silane, triazine silane, γ mercaptopropyitrimethoxy silane etc..
The silane coupled process layer can use epoxy silane, amino system silane, methacryloxy system silane, The formation such as silane couplers such as sulfydryl system silane.In addition, this silane coupler can also mix two or more use.Wherein, Preferably use amino system silane coupler or epoxy silane coupler is formed.
Amino system mentioned here silane coupler can be selected from by N- (2- amino-ethyls) -3- aminopropyl trimethoxies Silane, 3- (N- styrylmethyl -2- aminoethylaminos) propyl trimethoxy silicane, 3- aminopropyl triethoxysilicanes Alkane, double (2- hydroxyethyls)-APTESs, TSL 8330, N- dimethylaminopropyls Trimethoxy silane, N- phenyl amino propyls trimethoxy silane, N- (3- acryloxy -2- hydroxypropyls) -3- aminopropans Ethyl triethoxy silicane alkane, 4- ammobutyltriethoxysilanes, (aminoethylaminomethyl) phenethyl trimethoxy silane, N- (2- amino-ethyl -3- aminopropyls) trimethoxy silane, N- (2- amino-ethyl -3- aminopropyls) three (2- ethyl hexyl oxies) Silane, 6- (aminohexylaminopropyl) trimethoxy silane, aminophenyl trimethoxy silane, 3- (1- amino propoxyl group)- 3,3- dimethyl -1- acrylic trimethoxy silanes, 3- aminopropyls three (methoxyethoxyethoxy) silane, 3- aminopropans Ethyl triethoxy silicane alkane, 3- TSL 8330s, omega-amino undecyltrimethoxysilane, 3- (2-N- hexyls Aminoethylaminopropyl) trimethoxy silane, double (2- hydroxyethyls)-APTESs, (N, N- diethyl Base -3- aminopropyls) trimethoxy silane, (N, N- dimethyl -3- aminopropyls) trimethoxy silane, N- dimethylaminopropyls Trimethoxy silane, N- phenyl amino propyls trimethoxy silane, 3- (N- styrylmethyl -2- aminoethylaminos) propyl group Trimethoxy silane, γ aminopropyltriethoxy silane, N- β (amino-ethyl) gamma-aminos propyl trimethoxy silicane, N- The group that 3- (4- (3- amino propoxyl group) butoxy) propyl group -3- TSL 8330s are constituted.
Silane coupled process layer is preferably with silicon atom conversion in 0.05mg/m2~200mg/m2, preferably 0.15mg/m2 ~20mg/m2, preferably 0.3mg/m2~2.0mg/m2In the range of set.In the case of in the scope, can further it carry The adaptation of high base material and surface treatment copper foil.
In addition, to very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupled process layer or chromating layer Surface can carry out International Publication numbering WO2008/053878, Japanese Patent Laid-Open 2008-111169, Japanese Patent No. No. 5024930, International Publication numbering WO2006/028207, Japanese Patent No. 4828427, International Publication numbering WO2006/ 134868th, Japanese Patent No. 5046927, International Publication numbering WO2007/105635, Japanese Patent No. 5180815, Japan Surface treatment described in open patent 2013-19056.
In addition, the present invention appendix body copper foil can also in the very thin layers of copper or the roughening treatment layer on, Or possess resin bed in the refractory layer, antirust coat or chromating layer or silane coupled process layer.The tree Lipid layer can also be insulating resin layer.
The resin bed can be the insulation tree of adhesive or the semi-hardened state (B-stage state) of bonding Lipid layer.Semi-hardened state (B-stage state) includes following state：Insulating resin layer surface is touched using finger also not adhere to Sense, can be by the overlapping keeping of the insulating resin layer, if further heated processing, can produce sclerous reaction.
In addition, the resin bed can contain thermosetting resin or thermoplastic resin.In addition, the resin Layer can also contain thermoplastic resin.Its species is not particularly limited, and as suitable resin, for example, can be enumerated：Comprising Epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compound, polyvinyl acetal tree Fat, polyurethane resin, polyether sulfone, polyethersulfone resin, aromatic polyamide resin, polyamide-imide resin, rubber become cyclization Oxygen tree fat, phenoxy resin, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, heat are hard The resin of the property changed polyphenylene oxide resin, cyanate ester based resin, the acid anhydride of polybasic carboxylic acid etc..
The resin bed can also (can comprising known resin, hardening of resin agent, compound, hardening accelerator, dielectric medium To use any dielectric such as the dielectric medium comprising inorganic compound and/or organic compound, dielectric medium comprising metal oxide Matter), catalysts, crosslinking agent, polymer, prepreg, framework material etc..In addition, the resin bed can also be used for example International Publication numbering WO2008/004399, International Publication numbering WO2008/053878, International Publication numbering WO2009/ 084533rd, Japanese Patent Laid-Open 11-5828, Japanese Patent Laid-Open 11-140281, Japanese Patent No. 3184485, International Publication numbering WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open 2000-43188, Japan Patent No. 3612594, Japanese Patent Laid-Open 2002-179772, Japanese Patent Laid-Open 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open 2003-249739, Japanese Patent No. 4136509 Number, Japanese Patent Laid-Open 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, day This patent the 4286060th, Japanese Patent Laid-Open 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication numbering WO2004/ 005588th, Japanese Patent Laid-Open 2006-257153, Japanese Patent Laid-Open 2007-326923, Japanese Patent Laid-Open 2008- No. 111169, Japanese Patent No. 5024930, International Publication numbering WO2006/028207, Japanese Patent No. No. 4828427, day This patent JP 2009-67029, International Publication numbering WO2006/134868, Japanese Patent No. 5046927, Japan Patent JP 2009-173017, International Publication numbering WO2007/105635, Japanese Patent No. 5180815, International Publication numbering WO2008/114858, International Publication numbering WO2009/008471, Japanese Patent Laid-Open 2011-14727, International Publication numbering WO2009/001850, International Publication numbering WO2009/145179, International Publication numbering WO2011/068157, Japan Patent are special Open material (resin, hardening of resin agent, compound, hardening accelerator, dielectric medium, the catalytic reaction described in No. 2013-19056 Agent, crosslinking agent, polymer, prepreg, framework material etc.) and/or the forming method of resin bed, forming apparatus formed.
By these resins be for example dissolved in methyl ethyl ketone (MEK), toluene equal solvent and resin liquid is made, it is for example sharp Be coated on rolling method etc. in the very thin layers of copper or the refractory layer, antirust coat or the chromate skin membrane or Described in person on silane coupling agent layer, solvent is removed then according to heat drying is needed, B-stage state is made.As long as drying makes With such as hot-air drying stove just can, drying temperature be 100~250 DEG C, preferably 130~200 DEG C just may be used.
The copper foil (copper foil of the appendix body of attached resin) for possessing the appendix body of the resin bed is used with following form：Will After the resin bed and base material are overlapping, entirety is thermally compressed and makes the resin bed thermmohardening, then carrier is peeled off and exposed Very thin layers of copper (certainly, what is exposed is the surface of the intermediate layer side of the very thin layers of copper), and form specific wiring in very thin layers of copper Pattern.
If the copper foil of the appendix body using the attached resin, preimpregnation during manufacture multi-layer printed wiring base plate can be reduced The use piece number of body material.Furthermore, it is possible to the thickness of resin bed be set to be able to ensure that to the thickness of layer insulation, even if or complete Full copper clad laminate can also be manufactured without using prepreg material.In addition, now can also primary coat insulation tree on the surface of base material Fat further improves the flatness on surface.
In addition, in the case of without using prepreg material, there is following advantage：The material cost of prepreg material is saved, And lamination step also becomes simple, so economical advantages, in addition, the multilayer printed circuit manufactured with the thickness of prepreg material The thickness of substrate is thinning, and the thickness that can manufacture 1 layer is less than 100 μm of very thin multi-layer printed wiring base plate.
Preferably 0.1~80 μm of the thickness of the resin bed.If the thickness of resin bed is thinner than 0.1 μm, there is following situation：It is viscous Reduce with joint efforts, the copper foil of the appendix body of the attached resin is laminated to the base material for possessing inner layer material every prepreg material not being situated between When, it is difficult to ensure the layer insulation between the circuit of inner layer material.
On the other hand, if the thickness of resin bed is set to be thicker than 80 μm, it is difficult by 1 application step formation target The resin bed of thickness, can spend unnecessary fee of material and man-hour, so economically disadvantageous.Also, there is following situation：The tree of formation The flexibility of lipid layer is poor, so easily producing cracking etc. during operation, and excessive resin can be produced when being thermally compressed with inner layer material Flowing, it is difficult to be successfully laminated.
Also, another product form of the copper foil as the appendix body of the attached resin, can also in the very thin layers of copper, Or resin bed is utilized in the refractory layer, antirust coat or the chromating layer or the silane coupled process layer It is coated to, and is made after semi-hardened state, then peel off carrier, with the form system of the copper foil of the attached resin in the absence of carrier Make.
Hereinafter, some examples using the manufacturing step of the printed wiring board of the copper foil of the appendix body of the present invention are enumerated.
In an embodiment of the manufacture method of the printed wiring board of the present invention, comprise the following steps：Prepare the present invention Appendix body copper foil and insulated substrate；The copper foil and insulated substrate of the appendix body are laminated；And by the appendix body Copper foil and insulated substrate by very thin layers of copper side and insulated substrate are relative be laminated in the way of after, by peeling off the appendix body The step of carrier of copper foil and form copper clad laminate, semi-additive process, part addition process and subtract thereafter by semi-additive process, improvement Into any of method method formation circuit.Insulated substrate can also be set to be provided with the insulated substrate of internal layer circuit.
In the present invention, semi-additive process refers to carry out thin electroless plating on insulated substrate or copper foil inculating crystal layer, is formed After pattern, the method for forming conductive pattern using plating and etching.
Therefore, in the embodiment using the manufacture method of the printed wiring board of the invention of semi-additive process, including Following steps：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
The very thin layers of copper that the stripping carrier is exposed is utilized etching or plasma using etchant solutions such as acid etc. square Method is all removed；
In the resin for removing the very thin layers of copper by using etching and exposing, through hole and/or blind hole are set；
Removing glue Slag treatment is carried out to the region comprising the through hole and/or blind hole；
In the region comprising the resin and the through hole and/or blind hole, electroless plating is set；
Plating resist application is set on the electroless plating；
The plating resist application is exposed, the plating resist application in the region that power supply road is formed is removed thereafter；
The region formed on the power supply road for eliminating the plating resist application sets electro deposition；
Remove the plating resist application；And
The electroless plating on the region beyond the region that the power supply road is formed is removed using fast-etching etc..
In another embodiment using the manufacture method of the printed wiring board of the invention of semi-additive process, including it is as follows Step：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
The very thin layers of copper that the stripping carrier is exposed is utilized etching or plasma using etchant solutions such as acid etc. square Method is all removed；
On the surface for the resin for removing the very thin layers of copper by using etching and exposing, electroless plating is set；
Plating resist application is set on the electroless plating；
The plating resist application is exposed, the plating resist application in the region that power supply road is formed is removed thereafter；
The region formed on the power supply road for eliminating the plating resist application sets electro deposition；
Remove the plating resist application；And
The electroless plating and very thin copper on the region beyond the region that the power supply road is formed are removed using fast-etching etc. Layer.
In the present invention, improvement semi-additive process refers to following method：Laminated metal foil, utilizes plating resist application on the insulating layer Inverter circuit forming portion is protected, using plating is electrolysed in circuit forming portion copper facing, plating resist application is removed thereafter, (quick) etching is utilized The metal foil beyond the circuit forming portion is removed, circuit is thus formed on the insulating layer.
Therefore, in the embodiment using the manufacture method of the printed wiring board of the invention of improvement semi-additive process, Comprise the following steps：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
In the very thin layers of copper and insulated substrate peeled off the carrier and exposed, through hole and/or blind hole are set；
Removing glue Slag treatment is carried out to the region comprising the through hole and/or blind hole；
In the region comprising the through hole and/or blind hole, electroless plating is set；
On the very thin layers of copper surface peeled off the carrier and exposed, plating resist application is set；
Set after the plating resist application, circuit is formed using plating is electrolysed；
Remove the plating resist application；And
The very thin layers of copper by removing the plating resist application and exposing is removed using fast-etching.
In another embodiment using the manufacture method of the printed wiring board of the invention of improvement semi-additive process, including Following steps：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
Plating resist application is set on the very thin layers of copper that the carrier is exposed is peeled off；
The plating resist application is exposed, the plating resist application in the region that power supply road is formed is removed thereafter；
The region formed on the power supply road for eliminating the plating resist application sets electro deposition；
Remove the plating resist application；And
The electroless plating and very thin copper on the region beyond the region that the power supply road is formed are removed using fast-etching etc. Layer.
In the present invention, part addition process refers to following method：The substrate of conductor layer is being set, got through as needed Catalyst core is assigned on the substrate in the hole of through hole or perforation, is etched and forms conductor circuit, be arranged as required to After solder resist or plating resist application, through hole or perforation etc. are handled using electroless plating on the conductor circuit and carry out plating, by This manufacture printed wiring board.
Therefore, in the embodiment using the manufacture method of the printed wiring board of the invention of part addition process, bag Include following steps：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
Peeling off very thin layers of copper and insulated substrate setting through hole and/or blind hole that the carrier is exposed；
Removing glue Slag treatment is carried out to the region comprising the through hole and/or blind hole；
Catalyst core is assigned to the region comprising the through hole and/or blind hole；
On the very thin layers of copper surface peeled off the carrier and exposed, resist is set；
The resist is exposed and circuit pattern is formed；
The very thin layers of copper and the catalyst core are utilized into the methods such as the etching using etchant solutions such as acid or plasma Remove and form circuit；
Remove the resist；
The very thin layers of copper and the catalyst core are being utilized to the sides such as etching or plasma using etchant solutions such as acid The insulated substrate surface that method is removed and exposed sets solder resist or plating resist application；And
In the region for being not provided with the solder resist or plating resist application, electroless plating is set.
In the present invention, subtractive process refers to optionally remove not needing for the copper foil on copper clad laminate using etching etc. Part and the method that forms conductive pattern.
Therefore, in the embodiment using the manufacture method of the printed wiring board of the invention of subtractive process, including such as Lower step：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
In the very thin layers of copper and insulated substrate peeled off the carrier and exposed, through hole and/or blind hole are set；
Removing glue Slag treatment is carried out to the region comprising the through hole and/or blind hole；
In the region comprising the through hole and/or blind hole, electroless plating is set；
On the surface of the electroless plating, electro deposition is set；
On the surface of the electro deposition and/or the very thin layers of copper, resist is set；
The resist is exposed, circuit pattern is formed；
The very thin layers of copper and the electroless plating and the electro deposition are utilized to the etching using etchant solutions such as acid Or the method such as plasma removes and forms circuit；And
Remove the resist.
In another embodiment using the manufacture method of the printed wiring board of the invention of subtractive process, including following step Suddenly：
Prepare the copper foil and insulated substrate of the appendix body of the present invention；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the carrier of the copper foil of the appendix body is peeled off；
Peeling off very thin layers of copper and insulated substrate setting through hole and/or blind hole that the carrier is exposed；
Removing glue Slag treatment is carried out to the region comprising the through hole and/or blind hole；
In the region comprising the through hole and/or blind hole, electroless plating is set；
Shade is formed on the surface of the electroless plating；
On the surface for not forming the electroless plating of shade, electro deposition is set；
On the surface of the electro deposition and/or the very thin layers of copper, resist is set；
The resist is exposed and circuit pattern is formed；
The very thin layers of copper and the electroless plating are utilized into the methods such as the etching using etchant solutions such as acid or plasma Remove and form circuit；And
Remove the resist.
Can also be without setting through hole and/or blind hole the step of and subsequent de-smear step.
Here, using concrete example of the schema to the manufacture method of the printed wiring board of the copper foil of the appendix body using the present invention It is described in detail.In addition, here, being carried out exemplified by the copper foil of appendix body of roughening treatment layer is formd on very thin layers of copper surface Explanation, but it is also possible to do not form roughening treatment layer.
First, as shown in Fig. 1-A, prepare to form the copper foil of the appendix body of the very thin layers of copper of roughening treatment layer with surface (the 1st layer).
Then, as shown if figure 1-b, plating resist application is coated with the roughening treatment layer of very thin layers of copper, and is exposed, shows Shadow, specific shape is etched into by plating resist application.
Then, as shown in Fig. 1-C, after circuit coating is formed, plating resist application is removed, the electricity of given shape is consequently formed Road coating.
Then, as depicted in fig. 2-d, in the way of covering circuit coating (in the way of burying circuit coating) in very thin layers of copper It is upper set landfill resin and laminated resin layer, the copper foil (the 2nd layer) of another appendix body is then bonded from very thin layers of copper side.
Then, as shown in Fig. 2-E, carrier is peeled off from the copper foil of the 2nd layer of appendix body.
Then, as shown in Fig. 2-F, laser beam drilling is carried out in the ad-hoc location of resin bed, exposes circuit coating and forms blind Hole.
Then, as shown in Fig. 3-G, fill copper in blind hole and form through hole filler.
Then, as shown in Fig. 3-H, circuit coating is formed in the way of Fig. 1-B and Fig. 1-C on through hole filler.
Then, as shown in Fig. 3-I, carrier is peeled off from the copper foil of the 1st layer of appendix body.
Then, as shown in Fig. 4-J, the very thin layers of copper on two surfaces is removed using fast-etching, exposes the circuit in resin bed The surface of coating.
Then, as shown in Fig. 4-K, projection is formed on the circuit coating in resin bed, copper post is formed on the solder.With Mode as described above makes the printed wiring board of the copper foil of the appendix body using the present invention.
The copper foil (the 2nd layer) of the other appendix body can use the copper foil of the appendix body of the present invention, can also use The copper foil of conventional appendix body, and then common copper foil can also be used.Alternatively, it is also possible in the 2nd layer of circuit shown in Fig. 3-H Upper and then formation 1 layer or multilayer circuit, can also be by semi-additive process, subtractive process, part addition process or improvement semi-additive process Any method form these circuits.
In addition, the copper foil of appendix body used in described 1st layer can also be in the carrier side surface of the copper foil of the appendix body With substrate.By the way that with the substrate, the copper foil of appendix body is supported used in the 1st layer, is not likely to produce gauffer, so having The advantage of productivity lifting.As long as in addition, the substrate is with the effect for supporting the copper foil of appendix body used in described 1st layer Really, then all substrates can be used.For example, as the substrate, the carrier described in this case specification can be used, presoaked Body, resin bed or known carrier, prepreg, resin bed, metallic plate, metal foil, the plate of inorganic compound, inorganic compound Paper tinsel, the plate of organic compound, the paper tinsel of organic compound.
Time point on forming substrate in carrier side surface is not particularly limited, but must be formed before carrier is peeled off. Especially it is preferable over and is formed the step of very thin layers of copper side surface of the copper foil of the appendix body forms resin bed before, it is more excellent Select and formed in before the step of very thin layers of copper side surface of the copper foil in appendix body forms circuit.
In addition, landfill resin (resin) can use known resin, prepreg.BT can for example be used, and (span carrys out acyl Imines triazine) resin or prepreg, Ajinomoto Fine-Techno shares as the glass cloth for being impregnated with BT resins it is limited The ABF films or ABF of company's manufacture.In addition, the landfill resin can contain thermosetting resin or thermoplastic resin Fat.In addition, the landfill resin can also contain thermoplastic resin.The species of the landfill resin is not particularly limited, and is made For suitable resin, for example, it can enumerate：Include epoxy resin, polyimide resin, multi-functional cyanate esters, Malaysia Imide compound, polyvinyl acetal resin, polyurethane resin, block copolymerization polyimide resin, block copolymerization Polyimide resin, polyether sulfone, polyethersulfone resin, aromatic polyamide resin, polyamide-imide resin, rubber become epoxy Resin, phenoxy resin, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide-triazine resin, thermmohardening The resin of property polyphenylene oxide resin, cyanate ester based resin, the acid anhydride of polybasic carboxylic acid etc.；Or paper base material phenol resin, paper base material epoxy resin, Synthetic fibers cloth base material epoxy resin, glass cloth/paper composite base material epoxy resin, glass cloth/glass non-woven fabric composite base material ring Oxygen tree fat and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystalline polymer film, fluororesin film etc..In addition, institute Resin bed and/or resin and/or the prepreg described in this specification can be used by stating landfill resin (resin).
Also, by the printed wiring board electronic component mounting class in the present invention, so as to complete printed circuit board (PCB).In this hair In bright, " printed wiring board " also includes the printed wiring board and printed circuit board (PCB) and printing base for being equipped with electronic component class like this Plate.
Further, it is possible to use the printed wiring board makes e-machine, this can also be used to be equipped with electronic component class Print circuit plates making e-machine, can also use this to be equipped with the printed base plate of electronic component class and make e-machine.
In addition, the manufacture method of the printed wiring board of the present invention can also be the system of the printed wiring board comprised the following steps Make method (called non-sleeve method)：By the very thin layers of copper side surface of the copper foil of the appendix body of the present invention or the carrier side surface and tree Aliphatic radical plate is laminated；It is being opposite side with the very thin layers of copper side surface or the carrier side surface of the lamination of described and resin substrate Appendix body copper foil surface at least provided with this two layers of 1 resin bed and circuit；And formed the resin bed and circuit this After two layers, the carrier or the very thin layers of copper are peeled off from the copper foil of the appendix body.On the called non-sleeve method, specific example is used as Son, first, the very thin layers of copper side surface or carrier side surface of the copper foil of the appendix body of the present invention and resin substrate are laminated. Thereafter, in copper foil of the very thin layers of copper side surface or the carrier side surface with being laminated with resin substrate for the appendix body of opposite side Surface formed resin bed.The resin bed of carrier side surface or very thin layers of copper side surface can also be formed at from carrier side or pole Thin copper layer side and then the copper foil for being laminated another appendix body.In the case, as following composition：Centered on resin substrate, The resin substrate two face sides with the order of carrier/intermediate layer/very thin layers of copper or with very thin layers of copper/intermediate layer/carrier Order is laminated the copper foil of appendix body.The surface that can also be exposed in the very thin layers of copper or carrier at two ends sets another resin bed, And and then layers of copper or metal level are set, then the layers of copper or metal level are processed, circuit is consequently formed.Can also and then will Another resin bed is arranged in the way of filling the circuit on the circuit.Alternatively, it is also possible to by the shape of this circuit and resin bed Into more than 1 time (Layer increasing method) of progress.Also, can be with the layered product (hereinafter also referred to layered product B) formed in the above described manner The very thin layers of copper or carrier of the copper foil of each appendix body are peeled off from carrier or very thin layers of copper and coreless substrate is made.In addition, in system When making the coreless substrate, the copper foil of 2 appendix bodies can also be used, make it is following have very thin layers of copper/intermediate layer/carrier/ The layered product of the composition of carrier/intermediate layer/very thin layers of copper or with carrier/intermediate layer/very thin layers of copper/very thin layers of copper/centre The layered product of the composition of layer/carrier or composition with carrier/intermediate layer/very thin layers of copper/carrier/intermediate layer/very thin layers of copper Layered product, and the layered product is used for center.Can the both sides of these layered products (hereinafter also referred to layered product A) very thin copper The surface of layer or carrier sets this two layers of more than 1 time resin bed and circuit, is setting this two layers of more than 1 time resin bed and circuit Afterwards, the very thin layers of copper or carrier of the copper foil of each appendix body are peeled off from carrier or very thin layers of copper and makes coreless substrate.The layer Laminate is between the surface of very thin layers of copper, the surface of carrier, carrier and carrier, between very thin layers of copper and very thin layers of copper, very thin copper There can also be other layers between layer and carrier.In addition, in this specification, " surface of very thin layers of copper ", " very thin layers of copper side table Face ", " surface of carrier ", " carrier side surface ", " surface of layered product " are when very thin layers of copper, carrier, layered product are in very thin layers of copper In the case that surface, carrier surface, laminate surface have other layers, it is set to include other layers of the surface (most surface) Concept.In addition, layered product preferably has the composition of very thin layers of copper/intermediate layer/carrier/carrier/intermediate layer/very thin layers of copper.This is Due to：When making coreless substrate using the layered product, because configuring very thin layers of copper in coreless substrate side, easily use and change Good semi-additive process forms circuit on coreless substrate.In addition, being due to：Because the thickness of thin of very thin layers of copper, is easily removed The very thin layers of copper, removes and circuit is easily formed on coreless substrate using semi-additive process after very thin layers of copper.
" the layered product A " or " layered product B " " layered product " is represented extremely in addition, in this manual, be not recorded into especially Include layered product A and layered product B layered product less.
In addition, in the manufacture method of the coreless substrate, the copper foil or layered product of appendix body are covered by using resin Part or all of the end face of (layered product A), when manufacturing printed wiring board using Layer increasing method, can prevent decoction from penetrating into Between the copper foil of a piece of appendix body and the copper foil of another appendix body of intermediate layer or composition layered product, it can prevent by decoction The separation of very thin layers of copper and carrier caused by penetrating into or the corrosion of the copper foil of appendix body, can lift yield.It is used as institute here " some or all of resin of the end face of the copper foil of covering appendix body " that uses or " a part for the end face of coating laminate Or whole resins ", the resin that can be used in resin bed can be used.In addition, in the manufacture method of the coreless substrate, When overlooking the copper foil or layered product of appendix body, the copper foil of appendix body or laminated portion (carrier and the very thin copper of layered product Layer laminated portion or a piece of appendix body copper foil and another appendix body copper foil laminated portion) periphery at least one Part can be covered by resin or prepreg.In addition, layered product (the lamination formed using the manufacture method of the coreless substrate Body A) can also be that the copper foil for making a pair of appendix bodies is mutually contacted and constituted in a detachable fashion.In addition, to the appendix body Copper foil when being overlooked, the copper foil of appendix body or the laminated portion (carrier of layered product can also be covered by resin or prepreg With the laminated portion of very thin layers of copper or the laminated portion of the copper foil of the copper foil of a piece of appendix body and another appendix body) periphery It is overall.By being set to this composition, when overlooking the copper foil or layered product of appendix body, the lamination of the copper foil or layered product of appendix body Part is covered by resin or prepreg, and other parts can be prevented lateral, namely horizontal relative to laminating direction from the part Direction collision, as a result, can reduce operation in carrier and very thin layers of copper or appendix body copper foil it is mutual peel off.In addition, logical Cross in the way of the periphery for not exposing the copper foil of appendix body or the laminated portion of layered product and to be covered using resin or prepreg, Infiltration of the decoction process step Chinese medicine liquid as described above to the interface of the laminated portion can be prevented, the copper of appendix body can be prevented The corrosion or erosion of paper tinsel.In addition, when the copper foil of a pair of appendix bodies from layered product separates the copper foil of a piece of appendix body, or separation When carrier and copper foil (the very thin layers of copper) of the copper foil of appendix body, it is necessary to remove what is covered using resin or prepreg by cut-out etc. The copper foil of appendix body or layered product laminated portion (copper foil of the laminated portion or a piece of appendix body of carrier and very thin layers of copper and The laminated portion of the copper foil of another appendix body).
Can also by the copper foil of the appendix body of the present invention from carrier side or very thin layers of copper side be laminated to another it is of the invention The carrier side of the copper foil of appendix body or very thin layers of copper side and constitute layered product.Furthermore it is possible to be the copper foil of a piece of appendix body The carrier side surface or the very thin layers of copper side surface and another appendix body copper foil the carrier side surface Or the layered product that the very thin layers of copper side surface is obtained via adhesive contact laminating as needed.Alternatively, it is also possible to by institute State the carrier or pole thin copper layer Even of the carrier or very thin layers of copper of the copper foil of a piece of appendix body and the copper foil of another appendix body Connect.Here, the " Even connect " in the case where carrier or very thin layers of copper have surface-treated layer, also including via the surface-treated layer The form that Xiang Hu Even connect.Alternatively, it is also possible to covered by resin the layered product end face part or all.
The mutual lamination of carrier can for example be carried out in addition to merely overlapping using following methods.
(a) Ye Jin Even connect method：Welding (electric arc welding, TIG (tungsten inert gas, tungsten-inert gas) welderings Connect, MIG (metal inert gas, metal-noble gas) welding, resistance welding, seam welding, spot welding), crimping (ultrasonic Welding, friction stir weld), soldering；
(b) Ji Xie Even connect method：Ca(u)lk, using rivet Even connect and (connect, connect using rivet Even using self-pierce riveting Even), Binder；
(c) Wu Li Even connect method：Adhesive, (two-sided) adhesive tape
Entered by the way that part or all of part or all and another carrier of one carrier are connect into method using Suo Shu Even Row Even connects, and can manufacture a carrier and the lamination of another carrier, the layer for making carrier contact in a detachable fashion each other and constituting Laminate.If a carrier and another carrier weaker ground Even connect, in the case of by a carrier and the lamination of another carrier, even if not A carrier and another carrier Even socket parts are removed, a carrier and another carrier can also be separated.In addition, in a carrier and another In the case that carrier compare Qiang Di Even connect, cut-out or chemical grinding (erosion are utilized by the position for meeting a carrier and another Zai Ti Even Carve etc.), mechanical lapping etc. remove, a carrier and another carrier can be separated.
Furthermore it is possible to make printed wiring board by performing the following steps：In the layered product constituted in the above described manner extremely This two layers of 1 resin bed and circuit are set less；And after this two layers of 1 resin bed and circuit is at least formed, from the layer The copper foil of the appendix body of laminate peels off the very thin layers of copper or carrier.Alternatively, it is also possible on a surface of the layered product or two Individual surface sets this two layers of resin bed and circuit.
[embodiment]
Hereinafter, illustrated based on embodiment and comparative example.In addition, the present embodiment only one, and not only limit In the example.
1. manufacture the copper foil of appendix body
As foil carriers, (JX days ore deposit day stone metal companies are manufactured the electrolytic copper foil of the strip of 35 μm of thickness of preparation JTC) and 33 μm of thickness rolled copper foil (C1100 of JX days ore deposits day stone metal company manufacture).It is (bright to the glassy surface of the copper foil Face) under the following conditions using roller-to-roller type continuous plating wiring carry out nickel plating (Ni) or cobalt plating (Co) as metal-plated after, enter Row BTA processing is consequently formed intermediate layer as chromic acid salt treatment or using the processing of organic matter.In addition, " degreasing " of table 1, " acid Wash " represent to be utilized respectively following condition to carrier will the surface of nickel plating or cobalt plating side carry out the pre-treatment of nickel plating (Ni). Also, " polishing material " of table 1 is represented in following nickel plating (Ni) processing in the plating solution containing a polishing material (polishing material and secondary Polishing material).In addition, for embodiment 1,3,5,9,11, being heated after chromic acid salt treatment.By heating-up temperature now (drying temperature) is shown in table 1.In addition, sequentially carrying out degreasing, pickling processes to the surface of carrier.By the degreasing condition and pickling bar Part is shown in hereafter.
[degreasing]
Using following ungrease treatment liquid, electrolytic degreasing is carried out under the following conditions.
Ungrease treatment liquid：Sodium hydrate aqueous solution (naoh concentration 70g/L)
Electrolytic degreasing：Progress catholyte degreasing under the following conditions, followed by anode electrolysis degreasing, thereafter again Carry out catholyte degreasing.
Negative electrode (electrolysis) degreasing (current density 10A/dm2)：20 seconds
Anode (electrolysis) degreasing (current density 5A/dm2)：20 seconds
Negative electrode (electrolysis) degreasing (current density 10A/dm2)：20 seconds
[pickling]
Pickling processes liquid：Aqueous sulfuric acid (sulfuric acid concentration：50mL/L)
Dip time：20 seconds
[nickel plating (Ni)]
Plating solution
Nickel：20~200g/L
Boric acid：5~60g/L
Liquid temperature：40~65 DEG C
pH：1.5~5.0
Current density：0.5~20A/dm2
Conduction time：1~20 second
Stir (liquid internal circulating load)：100~1000L/ minutes
Travelling speed：2~30m/ minutes
Additive：Polishing material (saccharin sodium：0.5~5g/L), secondary polishing material (thiocarbamide：0.05~1g/L) [plating Cobalt (Co)]
Plating solution
Cobalt：20~200g/L
Boric acid：5~60g/L
Liquid temperature：40~65 DEG C
pH：1.5~5.0
Current density：0.5~20A/dm2
Conduction time：1~20 second
Stir (liquid internal circulating load)：100~1000L/ minutes
Travelling speed：2~30m/ minutes
Additive：Polishing material (saccharin sodium：0.5~5g/L), secondary polishing material (thiocarbamide：0.05~1g/L) [chromium Hydrochlorate processing]
Treatment fluid
Chromium：0.5~6.0g/L
Zinc：0.1~2.0g/L
Liquid temperature：25~60 DEG C
pH：2.5~5.0
Current density：0.1~4A/dm2
Conduction time：1~30 second
[BTA processing]
BTA processing：Use the antirust treatment of BTA
Treatment fluid
BTA：0.1~20g/L
pH：2~5
Liquid temperature：20~40 DEG C
Dip time：5~30 seconds
Then, by the continuous plating wiring of roller-to-roller type, being electroplated and being formed on the intermediate layer under the following conditions The very thin layers of copper of thickness described in table 1, so as to make the copper foil of appendix body.
Very thin layers of copper
Copper concentration：90~120g/L
H2SO4Concentration：20~120g/L
Electrolyte temperature：20~80 DEG C
Current density：10~70A/dm2
Plate liquidus flow velocity：1.0m/s
On these embodiments and comparative example, following roughening treatment is sequentially carried out to the surfaces of all very thin layers of copper, anti- Rust processing, chromic acid salt treatment and silane coupled processing.
Roughening treatment
Cu：10~20g/L
Co：5~15g/L
Ni：5~15g/L
pH：1~4
Temperature：40~50 DEG C
Current density Dk：40~50A/dm2
Time：0.5 second~2 seconds
Cu adhesion amounts：15~40mg/dm2
Co adhesion amounts：100~3000 μ g/dm2
Ni adhesion amounts：100~1000 μ g/dm2
Antirust treatment
Zn：0~20g/L
Ni：0~5g/L
pH：3.5
Temperature：40℃
Current density Dk：0~1.7A/dm2
Time：1 second
Zn adhesion amounts：5~250 μ g/dm2
Ni adhesion amounts：5~300 μ g/dm2
Antirust treatment
Zn：10g/L
Ni：35g/L
pH：3.5
Temperature：40℃
Current density Dk：0.5A/dm2
Time：46 seconds
Zn adhesion amounts：150~1500 μ g/dm2
Ni adhesion amounts：300~2600 μ g/dm2
Chromic acid salt treatment
Treatment fluid is constituted：
K2Cr2O7
(Na2Cr2O7Or CrO3)：2~10g/L
NaOH or KOH：10~50g/L
ZnO or ZnSO47H2O：0.05~10g/L
pH：7~13
Bath temperature：20~80 DEG C
Current density：0.05~5A/dm2
Time：5~30 seconds
Cr adhesion amounts：10~150 μ g/dm2
Silane coupled processing
The VTES aqueous solution
(VTES concentration：0.1~1.4wt%)
pH：4~5
Time：5~30 seconds
2. the assessment of the copper foil of appendix body
Various assessments are proceeded as described below to the embodiment and each sample of comparative example made in the manner.
The metal adhering amount in intermediate layer
Nickel adhesion amount and cobalt adhesion amount are to dissolve sample using the mass % of concentration 20 nitric acid, and use SII company systems The ICP emission spectrographic analysis device (models made：SPS3100) measured using ICP luminesceence analyses, zinc, chromium adhesion amount are logical Cross the dissolving with hydrochloric acid that sample is utilized to the mass % of concentration 7, the atomic absorption spectroscopy photometer (type manufactured using VARIAN companies Number：AA240FS) carry out quantitative analysis using atom light absorption method and measure.In addition, the nickel, cobalt, zinc, the measurement of chromium adhesion amount It is to be carried out using in the following manner.First, peeled off from the copper foil of appendix body after very thin layers of copper, only dissolve the intermediate layer side of very thin layers of copper Near surface (very thin layers of copper thickness be more than 1.4 μm in the case of, only dissolving the intermediate layer side away from very thin layers of copper table The μ m thick of face 0.5, very thin layers of copper thickness not up in the case of 1.4 μm, only table of the dissolving from the intermediate layer side of very thin layers of copper Face play very thin copper layer thickness 20%), measure the adhesion amount on the surface of the intermediate layer side of very thin layers of copper.In addition, peeling off pole After thin copper layer, only the near surface (away from the μ m thick of surface 0.5) of the intermediate layer side of dissolving carrier, measures the intermediate layer side of carrier The adhesion amount on surface.Also, by the surface of the adhesion amount on the surface of the intermediate layer side of very thin layers of copper and the intermediate layer side of carrier Adhesion amount amount to obtained by value be set to the metal adhering amount in intermediate layer.
Etching
The copper foil of appendix body is attached to BT resin substrates or FR-4 substrates and carries out heating in 2 hours with 220 DEG C and is crimped, Thereafter with 220 DEG C be heat-treated within 4 hours.Then, very thin layers of copper is peeled off from foil carriers.Then, it is very thin on substrate After layers of copper surface coating photonasty plating resist application, exposure, development step 50 L/S=10 μm/10 μm wide plating resist of formation are utilized Application pattern, goes down except the unnecessary portion of layers of copper in following spraying etching condition.
(spraying etching condition)
Etching solution：Ferric chloride in aqueous solution (Baume degrees：40 degree)
Liquid temperature：60℃
Spraying pressure：2.0MPa
Continue to etch, measuring circuit top width turns into 4 μm of time, and then assesses the length of circuit bottom width (Di side X now Degree) and etching coefficient.When being etched into sector (when producing turned-down edge), it is assumed that in the case that circuit is vertically etched from copper foil Drop wire is drawn on surface, in the case that the distance of the length of the turned-down edge from the intersection point of vertical line and resin substrate is set into a, etching system Number is the ratio for the thickness b for representing a and copper foil：B/a, the numerical value is bigger, it is meant that inclination angle is bigger, etching is not remained more residual Slag, turned-down edge is smaller.The schematic diagram of the cross section of the width of indication circuit pattern, and represent to use the schematic diagram in Figure 5 Etching coefficient computational methods outline.The a is by being measured from carrying out SEM above circuit, calculating etching coefficient (EF=b/a).In addition, being calculated using b=(X (μm) -4 (μm))/2., can be simply by using the etching coefficient Judge whether etching is good.In the present invention, it is that more than 2.5 to be set to etching good by etching coefficient, will be not up to 2.5 or nothing Method, which calculates and (is included in situation short-circuit between base part, adjacent circuit), is determined as that etching is abnormal, assesses per 1dm2Etching Abnormal number.
The covering rate of element beyond copper
The copper foil of appendix body is peeled off carrier/very thin layers of copper, carrier side is impregnated in ammonium sulfide solution.Sulphur Changing ammonium and having makes the property of Cu blackening, only copper carrier substrate not by Ni coating or Co coating etc. by the metal shape beyond copper Into the coat of metal or the covering of the layer such as chromating layer, organic matter layer part blackening.
Ammonium sulfide solution
Ammonium sulfide：5~20vol%
Liquid temperature：20~30 DEG C
Dip time：30 seconds~2 minutes
Thereafter, with scanner scanning carrier peel ply side, its image is processed into black and white with " 2 GTG ".By image White and black " threshold value " is set as that 70 is (white：0th, it is black：255) quilt for the element, the area occupation ratio of white portion being defined as beyond copper Cover rate.
Moisture yield (produced amount of moisture when the copper foil of appendix body is heated into 500 DEG C with 30 DEG C/min)
In the glove box replaced through argon gas, the copper foil of appendix body is cut into 9~20mm of φ size, from appendix body The carrier of copper foil peels off very thin layers of copper.After stripping, carrier and very thin layers of copper are imported into electronics science limited company simultaneously The heating of manufacture departs from the chamber of gas analyzing apparatus (TDS1200).The vacuum in chamber now is 2.0 × 10-7Pa Hereinafter, chamber indoor temperature is 30~60 DEG C.Then, 500 DEG C are warming up to 30 DEG C/min of speed, measured now produced Amount of moisture A (quality (g)).Amount of moisture be as appendix body copper foil per 1g moisture yield (quality (g)) (ppm) use under Formula is calculated.
Moisture yield (produced amount of moisture when the copper foil of appendix body is heated into 500 DEG C with 30 DEG C/min) (ppm/ G) quality (g) × 10 of the sample of the copper foil of=moisture yield A (quality (g))/measured appendix body6
The number of bulging
The copper foil of appendix body is heated 4 hours in 220 DEG C of atmospheric heating furnace.After heating, used using light microscope Visually count every 1dm2Bulging number.In addition, the copper foil of appendix body is heated into 10 points in 400 DEG C of atmospheric heating furnace Clock.After heating, using light microscope with visually counting every 1dm2Bulging number.
The experimental condition and result of the test are shown in table 1.
(assessment result)
The amount of moisture produced when the copper foil of appendix body is heated into 500 DEG C with 30 DEG C/min of embodiment 1~12 is all Below 160ppm/g, the generation of bulging and etching generation rate are all suppressed well.
In addition, embodiment 1~12 by the copper foil of appendix body with produced bulging during 220 DEG C of heating 4 hours all for 20/ dm2Hereinafter, the generation of moisture and etching generation rate are all suppressed well.
The amount of moisture produced when the copper foil of appendix body is heated into 500 DEG C with 30 DEG C/min of comparative example 1~3 is above 160ppm/g, the generation of bulging is all more, and etching generation rate is all bad.
In addition, the bulging produced when the copper foil of appendix body is heated 4 hours with 220 DEG C of comparative example 1~3 is above 20 Individual/dm2, the generation of moisture is all more, and etching generation rate is all bad.

Claims (133)

1. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using 30 DEG C/min be heated to 500 DEG C when produced amount of moisture as below 160ppm/g.
2. the copper foil of appendix body according to claim 1, wherein the copper foil of the appendix body is heated to 30 DEG C/min Produced amount of moisture is 0~130ppm/g at 500 DEG C.
3. the copper foil of appendix body according to claim 2, wherein the copper foil of the appendix body is heated to 30 DEG C/min Produced amount of moisture is 0~110ppm/g at 500 DEG C.
4. the copper foil of appendix body according to claim 1, wherein the copper foil of the appendix body is heated 4 hours with 220 DEG C When produced bulging be 20/dm2Below.
5. the copper foil of the appendix body according to Claims 2 or 3, wherein the copper foil of the appendix body is small with 220 DEG C of heating 4 Constantly produced bulging is 20/dm2Below.
6. the copper foil of appendix body according to any one of claim 1 to 4, wherein by the copper foil of the appendix body with 220 Produced bulging is 0~15/dm during DEG C heating 4 hours2Below.
7. the copper foil of appendix body according to any one of claim 1 to 4, wherein by the copper foil of the appendix body with 220 Produced bulging is 0~12/dm during DEG C heating 4 hours2Below.
8. the copper foil of appendix body according to claim 1, wherein the copper foil of the appendix body is heated 10 minutes with 400 DEG C When produced bulging be 0~60/dm2Below.
9. the copper foil of appendix body according to claim 1, wherein the copper foil of the appendix body is heated 10 minutes with 400 DEG C When produced bulging be 0~30/dm2Below.
10. the copper foil of appendix body according to claim 4, wherein the copper foil of the appendix body is heated into 10 points with 400 DEG C Produced bulging is 0~60/dm during clock2Below.
11. the copper foil of appendix body according to claim 4, wherein the copper foil of the appendix body is heated into 10 points with 400 DEG C Produced bulging is 0~30/dm during clock2Below.
12. the copper foil of appendix body according to claim 7, wherein the copper foil of the appendix body is heated into 10 points with 400 DEG C Produced bulging is 0~60/dm during clock2Below.
13. the copper foil of the appendix body according to Claims 2 or 3, wherein by the copper foil of the appendix body with 400 DEG C of heating 10 Produced bulging is 0~60/dm during minute2Below.
14. the copper foil of the appendix body according to any one of Claims 1-4,8 to 11, wherein choosing is contained in the intermediate layer It is free Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic It is more than one or both of group of thing composition.
15. the copper foil of appendix body according to claim 14, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
16. the copper foil of appendix body according to claim 14, wherein the organic matter be by selected from organic compounds containing nitrogen, The organic matter more than one or both of organic compounds containing sulfur and carboxylic acid constituted.
17. the copper foil of the appendix body according to any one of Claims 1-4,8 to 11, wherein in the very thin layers of copper table Any surface or two sides on face or the surface of the carrier have roughening treatment layer.
18. the copper foil of appendix body according to claim 17, wherein have on the surface of roughening treatment layer be selected from by The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
19. the copper foil of appendix body according to claim 18, wherein there is the refractory layer on roughening treatment layer.
20. the copper foil of appendix body according to claim 18, wherein at least one layer of the antirust coat and the refractory layer Contain the element selected from one or more of nickel, cobalt, copper, zinc.
21. the copper foil of appendix body according to claim 18, wherein having on roughening treatment layer or the refractory layer There is the antirust coat.
22. the copper foil of appendix body according to claim 18, wherein having the chromic acid salt treatment on the antirust coat Layer.
23. the copper foil of appendix body according to claim 18, wherein having the silane on the chromating layer Coupling processing layer.
24. the copper foil of the appendix body according to any one of Claims 1-4,8 to 11, wherein in the very thin layers of copper Surface has selected from one or more of group being made up of refractory layer, antirust coat, chromating layer and silane coupled process layer Layer.
25. the copper foil of the appendix body according to any one of Claims 1-4,8 to 11, wherein in the very thin layers of copper Possesses resin bed.
26. the copper foil of appendix body according to claim 17, wherein possessing resin bed on roughening treatment layer.
27. the copper foil of appendix body according to claim 18, wherein selected from by the refractory layer, antirust coat, chromate Possesses resin bed on the layer of one or more of the group of process layer and silane coupled process layer composition.
28. the copper foil of appendix body according to claim 25, wherein the resin bed contains dielectric medium.
29. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using produced bulging during 220 DEG C of heating 4 hours as 20/dm2Below.
30. the copper foil of appendix body according to claim 29, wherein the copper foil of the appendix body is small with 220 DEG C of heating 4 Constantly produced bulging is 0~15/dm2Below.
31. the copper foil of appendix body according to claim 29, wherein the copper foil of the appendix body is small with 220 DEG C of heating 4 Constantly produced bulging is 0~12/dm2Below.
32. the copper foil of appendix body according to claim 29, wherein the copper foil of the appendix body is heated into 10 points with 400 DEG C Produced bulging is 0~60/dm during clock2Below.
33. the copper foil of the appendix body according to claim 30 or 31, wherein by the copper foil of the appendix body with 400 DEG C of heating Produced bulging is 0~60/dm at 10 minutes2Below.
34. the copper foil of appendix body according to claim 31, wherein the intermediate layer is in the case of containing Cr, contains 5 μ g/dm2The μ g/dm of the above 1002Following Cr, in the case of containing Mo, contains 50 μ g/dm2The μ g/dm of the above 10002Following Mo, in the case of containing Ni, contains 100 μ g/dm2The μ g/dm of the above 400002Following Ni, in the case of containing Co, contains 100μg/dm2The μ g/dm of the above 400002Following Co, in the case of containing Zn, contains 1 μ g/dm2The μ g/dm of the above 1202Below Zn.
35. the copper foil of the appendix body according to any one of claim 29 to 32, wherein the intermediate layer contain selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic matter group Into one or both of group more than.
36. the copper foil of appendix body according to claim 35, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
37. the copper foil of appendix body according to claim 35, wherein the organic matter be by selected from organic compounds containing nitrogen, The organic matter more than one or both of organic compounds containing sulfur and carboxylic acid constituted.
38. the copper foil of the appendix body according to any one of claim 29 to 32, wherein on the very thin layers of copper surface or Any surface on the surface of the carrier or two sides have roughening treatment layer.
39. the copper foil of the appendix body according to claim 38, wherein have on the surface of roughening treatment layer be selected from by The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
40. the copper foil of the appendix body according to claim 39, wherein there is the refractory layer on roughening treatment layer.
41. the copper foil of the appendix body according to claim 39, wherein at least one layer of the antirust coat and the refractory layer Contain the element selected from one or more of nickel, cobalt, copper, zinc.
42. the copper foil of the appendix body according to claim 39, wherein having on roughening treatment layer or the refractory layer There is the antirust coat.
43. the copper foil of the appendix body according to claim 39, wherein having the chromic acid salt treatment on the antirust coat Layer.
44. the copper foil of the appendix body according to claim 39, wherein having the silane on the chromating layer Coupling processing layer.
45. the copper foil of the appendix body according to any one of claim 29 to 32, wherein on the surface of the very thin layers of copper With the layer selected from one or more of the group being made up of refractory layer, antirust coat, chromating layer and silane coupled process layer.
46. the copper foil of the appendix body according to any one of claim 29 to 32, wherein possessing in the very thin layers of copper Resin bed.
47. the copper foil of the appendix body according to claim 38, wherein possessing resin bed on roughening treatment layer.
48. the copper foil of the appendix body according to claim 39, wherein selected from by the refractory layer, antirust coat, chromate Possesses resin bed on the layer of one or more of the group of process layer and silane coupled process layer composition.
49. the copper foil of appendix body according to claim 46, wherein the resin bed contains dielectric medium.
50. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using produced bulging during 400 DEG C of heating 10 minutes as 0~60/dm2Below.
51. the copper foil of appendix body according to claim 50, wherein the intermediate layer contain selected from by Cr, Ni, Co, Fe, One in Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition Plant or two or more.
52. the copper foil of appendix body according to claim 51, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
53. the copper foil of appendix body according to claim 51, wherein the organic matter be by selected from organic compounds containing nitrogen, The organic matter more than one or both of organic compounds containing sulfur and carboxylic acid constituted.
54. the copper foil of appendix body according to claim 50, wherein in the very thin layers of copper surface or the table of the carrier Any surface in face or two sides have roughening treatment layer.
55. the copper foil of appendix body according to claim 54, wherein have on the surface of roughening treatment layer be selected from by The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
56. the copper foil of appendix body according to claim 55, wherein there is the refractory layer on roughening treatment layer.
57. the copper foil of appendix body according to claim 55, wherein at least one layer of the antirust coat and the refractory layer Contain the element selected from one or more of nickel, cobalt, copper, zinc.
58. the copper foil of appendix body according to claim 55, wherein having on roughening treatment layer or the refractory layer There is the antirust coat.
59. the copper foil of appendix body according to claim 55, wherein having the chromic acid salt treatment on the antirust coat Layer.
60. the copper foil of appendix body according to claim 55, wherein having the silane on the chromating layer Coupling processing layer.
61. the copper foil of appendix body according to claim 50, is selected from by resistance to wherein having on the surface of the very thin layers of copper The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are constituted.
62. the copper foil of appendix body according to claim 50, wherein possessing resin bed in the very thin layers of copper.
63. the copper foil of appendix body according to claim 54, wherein possessing resin bed on roughening treatment layer.
64. the copper foil of appendix body according to claim 55, wherein selected from by the refractory layer, antirust coat, chromate Possesses resin bed on the layer of one or more of the group of process layer and silane coupled process layer composition.
65. the copper foil of appendix body according to claim 62, wherein the resin bed contains dielectric medium.
66. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using produced bulging during 400 DEG C of heating 10 minutes as 0~50/dm2Below.
67. the copper foil of appendix body according to claim 66, wherein the intermediate layer contain selected from by Cr, Ni, Co, Fe, One in Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition Plant or two or more.
68. the copper foil of appendix body according to claim 67, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
69. the copper foil of appendix body according to claim 67, wherein the organic matter be by selected from organic compounds containing nitrogen, The organic matter more than one or both of organic compounds containing sulfur and carboxylic acid constituted.
70. the copper foil of appendix body according to claim 66, wherein in the very thin layers of copper surface or the table of the carrier Any surface in face or two sides have roughening treatment layer.
71. the copper foil of appendix body according to claim 70, wherein have on the surface of roughening treatment layer be selected from by The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
72. the copper foil of the appendix body according to claim 71, wherein there is the refractory layer on roughening treatment layer.
73. the copper foil of the appendix body according to claim 71, wherein at least one layer of the antirust coat and the refractory layer Contain the element selected from one or more of nickel, cobalt, copper, zinc.
74. the copper foil of the appendix body according to claim 71, wherein having on roughening treatment layer or the refractory layer There is the antirust coat.
75. the copper foil of the appendix body according to claim 71, wherein having the chromic acid salt treatment on the antirust coat Layer.
76. the copper foil of the appendix body according to claim 71, wherein having the silane on the chromating layer Coupling processing layer.
77. the copper foil of appendix body according to claim 66, is selected from by resistance to wherein having on the surface of the very thin layers of copper The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are constituted.
78. the copper foil of appendix body according to claim 66, wherein possessing resin bed in the very thin layers of copper.
79. the copper foil of appendix body according to claim 70, wherein possessing resin bed on roughening treatment layer.
80. the copper foil of the appendix body according to claim 71, wherein selected from by the refractory layer, antirust coat, chromate Possesses resin bed on the layer of one or more of the group of process layer and silane coupled process layer composition.
81. the copper foil of the appendix body according to claim 78, wherein the resin bed contains dielectric medium.
82. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using produced bulging during 400 DEG C of heating 10 minutes as 0~40/dm2Below.
83. the copper foil of the appendix body according to claim 82, wherein the intermediate layer contain selected from by Cr, Ni, Co, Fe, One in Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition Plant or two or more.
84. the copper foil of the appendix body according to claim 83, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
85. the copper foil of the appendix body according to claim 83, wherein the organic matter be by selected from organic compounds containing nitrogen, The organic matter more than one or both of organic compounds containing sulfur and carboxylic acid constituted.
86. the copper foil of the appendix body according to claim 82, wherein in the very thin layers of copper surface or the table of the carrier Any surface in face or two sides have roughening treatment layer.
87. the copper foil of the appendix body according to claim 86, wherein have on the surface of roughening treatment layer be selected from by The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupled process layer are constituted.
88. the copper foil of the appendix body according to claim 87, wherein there is the refractory layer on roughening treatment layer.
89. the copper foil of the appendix body according to claim 87, wherein at least one layer of the antirust coat and the refractory layer Contain the element selected from one or more of nickel, cobalt, copper, zinc.
90. the copper foil of the appendix body according to claim 87, wherein having on roughening treatment layer or the refractory layer There is the antirust coat.
91. the copper foil of the appendix body according to claim 87, wherein having the chromic acid salt treatment on the antirust coat Layer.
92. the copper foil of the appendix body according to claim 87, wherein having the silane on the chromating layer Coupling processing layer.
93. the copper foil of the appendix body according to claim 82, is selected from by resistance to wherein having on the surface of the very thin layers of copper The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are constituted.
94. the copper foil of the appendix body according to claim 82, wherein possessing resin bed in the very thin layers of copper.
95. the copper foil of the appendix body according to claim 86, wherein possessing resin bed on roughening treatment layer.
96. the copper foil of the appendix body according to claim 87, wherein selected from by the refractory layer, antirust coat, chromate Possesses resin bed on the layer of one or more of the group of process layer and silane coupled process layer composition.
97. the copper foil of the appendix body according to claim 94, wherein the resin bed contains dielectric medium.
98. a kind of copper foil of appendix body, it sequentially possesses carrier, intermediate layer and very thin layers of copper,
By the copper foil of the appendix body using produced bulging during 400 DEG C of heating 10 minutes as 0~30/dm2Below.
99. the copper foil of the appendix body according to claim 98, wherein the intermediate layer contain selected from by Cr, Ni, Co, Fe, One in Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, the group of organic matter composition Plant or two or more.
100. the copper foil of the appendix body according to claim 99, wherein the intermediate layer is with more than 25nm below 80nm thickness Degree contains organic matter.
101. the copper foil of the appendix body according to claim 99, wherein the organic matter is by selected from nitrogenous organic compound The organic matter more than one or both of thing, organic compounds containing sulfur and carboxylic acid constituted.
102. the copper foil of the appendix body according to claim 98, wherein in the very thin layers of copper surface or the table of the carrier Any surface in face or two sides have roughening treatment layer.
103. the copper foil of the appendix body according to claim 102, is selected from wherein having on the surface of roughening treatment layer The layer of one or more of the group being made up of refractory layer, antirust coat, chromating layer and silane coupled process layer.
104. the copper foil of the appendix body according to claim 103, wherein having on roughening treatment layer described heat-resisting Layer.
105. the copper foil of the appendix body according to claim 103, wherein at least the one of the antirust coat and the refractory layer Layer contains the element selected from one or more of nickel, cobalt, copper, zinc.
106. the copper foil of the appendix body according to claim 103, wherein on roughening treatment layer or the refractory layer With the antirust coat.
107. the copper foil of the appendix body according to claim 103, wherein having on the antirust coat at the chromate Manage layer.
108. the copper foil of the appendix body according to claim 103, wherein having the silicon on the chromating layer Alkane coupling processing layer.
109. the copper foil of the appendix body according to claim 98, is selected from by resistance to wherein having on the surface of the very thin layers of copper The layer of one or more of the group that thermosphere, antirust coat, chromating layer and silane coupled process layer are constituted.
110. the copper foil of the appendix body according to claim 98, wherein possessing resin bed in the very thin layers of copper.
111. the copper foil of the appendix body according to claim 102, wherein possessing resin bed on roughening treatment layer.
112. the copper foil of the appendix body according to claim 103, wherein selected from by the refractory layer, antirust coat, chromic acid Possesses resin bed on the layer of one or more of the group of salt treatment layer and silane coupled process layer composition.
113. the copper foil of the appendix body according to claim 110, wherein the resin bed contains dielectric medium.
114. a kind of printed wiring board, usage right requires the copper foil of the appendix body any one of 1 to 113 and manufactured.
115. a kind of copper clad laminate, usage right requires the copper foil of the appendix body any one of 1 to 113 and manufactured.
116. a kind of e-machine, usage right requires the printed wiring board described in 114 and manufactured.
117. a kind of layered product, usage right requires the copper foil of the appendix body any one of 1 to 113 and manufactured.
118. a kind of layered product, copper foil and resin containing the appendix body any one of claim 1 to 113 are described attached Part or all of the end face of the copper foil of carrier is covered by the resin.
119. a kind of layered product, by the copper foil of the appendix body any one of a piece of claim 1 to 113 from the carrier side Or the very thin layers of copper side is laminated to the load of the copper foil of the appendix body any one of another claim 1 to 113 Side or the very thin layers of copper side are formed.
120. the layered product according to claim 119, by the carrier side surface of the copper foil of a piece of appendix body or The carrier side surface of the copper foil of the very thin layers of copper side surface and another appendix body or the very thin layers of copper side table Face is constituted via adhesive contact laminating as needed.
121. the layered product according to claim 119, wherein the carrier or described of the copper foil of a piece of appendix body The carrier of the copper foil of very thin layers of copper and another appendix body or the pole thin copper layer Even connect.
122. a kind of manufacture method of printed wiring board, the layered product any one of usage right requirement 117 to 121.
123. the layered product according to any one of claim 119 to 121 a, wherein part for the end face of the layered product Or all covered by resin.
124. a kind of manufacture method of printed wiring board, comprises the following steps：
In the layered product any one of claim 119 to 121 at least provided with this two layers of 1 resin bed and circuit；And
After this two layers of 1 resin bed and circuit is at least formed, peeled off from the copper foil of the appendix body of the layered product described Very thin layers of copper or the carrier.
125. a kind of manufacture method of printed wiring board, comprises the following steps：
In the layered product described in claim 123 at least provided with this two layers of 1 resin bed and circuit；And
After this two layers of 1 resin bed and circuit is at least formed, peeled off from the copper foil of the appendix body of the layered product described Very thin layers of copper or the carrier.
126. a kind of manufacture method of printed wiring board, comprises the following steps：
Prepare the copper foil and insulated substrate of the appendix body any one of claim 1 to 113；
The copper foil and insulated substrate of the appendix body are laminated；
After the copper foil and insulated substrate of the appendix body are laminated, the foil carriers of the copper foil by peeling off the appendix body The step of and form copper clad laminate,
Thereafter, any of semi-additive process, subtractive process, part addition process or improvement semi-additive process method formation circuit are passed through.
127. a kind of manufacture method of printed wiring board, comprises the following steps：
In the very thin layers of copper side of the copper foil of the appendix body any one of claim 1 to 113 or the carrier side table Face forms circuit；
In the way of burying the circuit the appendix body copper foil the very thin layers of copper side surface or the carrier side shape Resin layer；
Circuit is formed on the resin bed；
Formed on the resin bed after circuit, peel off the carrier or the very thin layers of copper；And
Peel off after the carrier or the very thin layers of copper, by removing the very thin layers of copper or the carrier, and make to be formed in institute The circuit being buried in the resin bed for stating very thin layers of copper side surface or the carrier side surface exposes.
128. the manufacture method of the printed wiring board according to claim 127, wherein described form circuit on the resin layer The step of be to be fitted in the copper foil of other appendix body on the resin bed from very thin layers of copper side or carrier side, using being fitted in The copper foil of the appendix body of the resin bed and the step of form the circuit.
129. the manufacture method of the printed wiring board according to claim 128, wherein it is described be fitted on resin bed it is another The copper foil of outer appendix body is the copper foil of the appendix body any one of claim 1 to 113.
130. the manufacture method of the printed wiring board according to claim 127, wherein described form circuit on the resin layer The step of can pass through semi-additive process, subtractive process, part addition process or improvement any of semi-additive process method and carry out.
131. the manufacture method of the printed wiring board according to claim 127, wherein described will be in circuit forming surface The copper foil of appendix body has substrate on the surface on the surface of the carrier side of the copper foil of the appendix body or very thin layers of copper side.
132. a kind of manufacture method of printed wiring board, comprises the following steps：
By the very thin layers of copper side surface of the copper foil of the appendix body any one of claim 1 to 113 and resin substrate It is laminated；
At least set for the carrier side surface of opposite side in the copper foil of the appendix body and with the side that resin substrate is laminated Put this two layers of 1 resin bed and circuit；And
At least formed after this two layers of 1 resin bed and circuit, the very thin layers of copper is peeled off from the copper foil of the appendix body.
133. a kind of manufacture method of printed wiring board, comprises the following steps：
The carrier side surface of the copper foil of appendix body any one of claim 1 to 113 and resin substrate are carried out Lamination；
At least set for the very thin layers of copper side surface of opposite side in the copper foil of the appendix body and with the side that resin substrate is laminated Put this two layers of 1 resin bed and circuit；And
At least formed after this two layers of 1 resin bed and circuit, the carrier is peeled off from the copper foil of the appendix body.
CN201510147943.1A 2014-03-31 2015-03-31 The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board Active CN104943270B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014073870 2014-03-31
JP2014-073841 2014-03-31
JP2014073841 2014-03-31
JP2014-073870 2014-03-31

Publications (2)

Publication Number Publication Date
CN104943270A CN104943270A (en) 2015-09-30
CN104943270B true CN104943270B (en) 2017-10-31

Family

ID=54158578

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510147943.1A Active CN104943270B (en) 2014-03-31 2015-03-31 The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board

Country Status (4)

Country Link
JP (1) JP6342356B2 (en)
KR (1) KR101705969B1 (en)
CN (1) CN104943270B (en)
TW (1) TWI613940B (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6570430B2 (en) * 2015-11-12 2019-09-04 Ｊｘ金属株式会社 Method for producing copper foil with carrier, method for producing printed wiring board, and method for producing electronic device
JP2017124533A (en) * 2016-01-13 2017-07-20 Ｊｘ金属株式会社 Copper foil with carrier, laminate, method for manufacturing copper foil with carrier, method for manufacturing printed wiring board, and method for manufacturing electric equipment
CN105704948B (en) * 2016-03-28 2018-05-29 上海美维电子有限公司 The production method of ultra-thin printed circuit board and ultra-thin printed circuit board
JP2017177610A (en) * 2016-03-30 2017-10-05 Ｊｘ金属株式会社 Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device
JP2017177611A (en) * 2016-03-30 2017-10-05 Ｊｘ金属株式会社 Copper foil with carrier, laminate, manufacturing method of printed wiring board and manufacturing method of electronic device
JP6391621B2 (en) * 2016-03-31 2018-09-19 Ｊｘ金属株式会社 Titanium copper foil, copper products, electronic equipment parts and autofocus camera module
KR101881287B1 (en) * 2017-01-16 2018-07-27 일진머티리얼즈 주식회사 Copper foil attached to the carrier foil
CN107623990A (en) * 2017-07-26 2018-01-23 珠海亚泰电子科技有限公司 Thicken copper base and preparation technology
CN108093572A (en) * 2017-12-15 2018-05-29 上海美维科技有限公司 A kind of production method of the printed circuit board with no porose disc blind hole structure
JP6462940B1 (en) * 2018-03-23 2019-01-30 三井金属鉱業株式会社 Copper foil with carrier, copper-clad laminate and printed wiring board
CN112423982A (en) * 2018-07-18 2021-02-26 昭和电工材料株式会社 Copper-clad laminate, printed wiring board, semiconductor package, and method for manufacturing copper-clad laminate
JP7328671B2 (en) * 2019-05-09 2023-08-17 ナミックス株式会社 laminate
US10697082B1 (en) * 2019-08-12 2020-06-30 Chang Chun Petrochemical Co., Ltd. Surface-treated copper foil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1383705A (en) * 2000-07-07 2002-12-04 三井金属鉱业株式会社 Carrier-field copper foil circuit, printed circuit board mfg. method using circuit, and printed circuit board
CN103392028A (en) * 2011-08-31 2013-11-13 Jx日矿日石金属株式会社 Copper foil with carrier
WO2014017606A1 (en) * 2012-07-25 2014-01-30 Jx日鉱日石金属株式会社 Copper foil with carrier

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0818401B2 (en) * 1989-05-17 1996-02-28 福田金属箔粉工業株式会社 Composite foil and its manufacturing method
JP4160131B2 (en) * 1994-12-26 2008-10-01 日立化成工業株式会社 Method for producing metal foil for printed wiring board
JP2001127429A (en) * 1999-10-25 2001-05-11 Hitachi Chem Co Ltd Method for producing multilayer printed wiring board
US7691487B2 (en) 2002-07-04 2010-04-06 Mitsui Mining & Smelting Co., Ltd. Electrodeposited copper foil with carrier foil
JP4701735B2 (en) * 2004-07-09 2011-06-15 株式会社豊田自動織機 Sliding member
JP4429979B2 (en) 2005-06-29 2010-03-10 古河電気工業株式会社 Ultra-thin copper foil with carrier and method for producing ultra-thin copper foil with carrier
JP4927503B2 (en) * 2005-12-15 2012-05-09 古河電気工業株式会社 Ultra-thin copper foil with carrier and printed wiring board
WO2007111268A1 (en) * 2006-03-24 2007-10-04 Ube Industries, Ltd. Process for producing copper wiring polyimide film, and copper wiring polyimide film
JP2010006071A (en) 2009-08-21 2010-01-14 Furukawa Electric Co Ltd:The Surface treatment copper foil, extremely thin copper foil with carrier, flexible copper clad laminate, and polyimide based flexible printed wiring board
US8329315B2 (en) * 2011-01-31 2012-12-11 Nan Ya Plastics Corporation Ultra thin copper foil with very low profile copper foil as carrier and its manufacturing method
TWI511633B (en) * 2011-03-30 2015-12-01 Mitsui Mining & Smelting Co Method of manufacturing multi-layer printed wiring board and multi-layer printed wiring board obtained by the manufacturing method
JP2013001993A (en) * 2011-06-21 2013-01-07 Meltex Inc Ultrathin copper foil with carrier foil and method of manufacturing the same
JP5413693B2 (en) * 2012-02-06 2014-02-12 日立化成株式会社 Circuit forming support substrate and method of manufacturing semiconductor device mounting package substrate
KR101391811B1 (en) * 2012-08-17 2014-05-07 일진머티리얼즈 주식회사 Copper foil attached to the carrier foil, copper-clad laminate and printed circuit board using the same
JP5481577B1 (en) * 2012-09-11 2014-04-23 Ｊｘ日鉱日石金属株式会社 Copper foil with carrier
JP5521099B1 (en) * 2013-09-02 2014-06-11 Ｊｘ日鉱日石金属株式会社 Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1383705A (en) * 2000-07-07 2002-12-04 三井金属鉱业株式会社 Carrier-field copper foil circuit, printed circuit board mfg. method using circuit, and printed circuit board
CN103392028A (en) * 2011-08-31 2013-11-13 Jx日矿日石金属株式会社 Copper foil with carrier
WO2014017606A1 (en) * 2012-07-25 2014-01-30 Jx日鉱日石金属株式会社 Copper foil with carrier

Also Published As

Publication number Publication date
JP6342356B2 (en) 2018-06-13
TWI613940B (en) 2018-02-01
TW201542047A (en) 2015-11-01
KR20150113901A (en) 2015-10-08
JP2015199355A (en) 2015-11-12
CN104943270A (en) 2015-09-30
KR101705969B1 (en) 2017-02-10

Similar Documents

Publication Publication Date Title
CN104943270B (en) The copper foil of appendix body, printed wiring board, layered product, the manufacture method of e-machine and printed wiring board
CN106455341B (en) The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine
CN106455342B (en) The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine
CN104717831B (en) Surface treatment copper foil, laminate, printed wiring board, e-machine, the manufacture method of Copper foil with carrier and printed wiring board
US10187983B2 (en) Copper foil provided with carrier, laminate, printed wiring board, electronic device, and method for fabricating printed wiring board
CN106455310B (en) The manufacturing method of Copper foil with carrier, laminate, the manufacturing method of printing distributing board and e-machine
CN106358377B (en) Copper foil with carrier, laminate, the manufacturing method of laminate, the manufacturing method of the manufacturing method of printing distributing board and e-machine
JP5228130B1 (en) Copper foil with carrier
CN105209252B (en) Copper foil with carrier, the manufacture method using its copper-cover laminated plate, printing distributing board, e-machine and printing distributing board
TW201800242A (en) Surface-treated copper foil and copper-clad laminate produced using same
CN105007687B (en) The manufacturing method of Copper foil with carrier, printing distributing board, laminate, e-machine and printing distributing board
CN105408524A (en) Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper-clad laminate, and method for manufacturing printed circuit board
TWI694180B (en) Surface-treated copper foil, surface-treated copper foil with resin layer, copper foil with carrier, laminate, printed wiring board manufacturing method, and electronic device manufacturing method
CN104943255A (en) Surface processing copper foil, bonding copper lamination plate, printed distribution board, electronic device, semiconductor package and making method of the printed distribution board
CN105835478B (en) Surface treatment copper foil and product about it
JP5997080B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
CN106304614A (en) The manufacture method of Copper foil with carrier, laminate, printing distributing board, e-machine and printing distributing board
JP5298252B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5386652B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6821370B2 (en) Metal foil with carrier, laminate, manufacturing method of laminate, manufacturing method of printed wiring board and manufacturing method of electronic equipment
JP6842232B2 (en) Manufacturing method of metal foil with carrier, laminate, printed wiring board, electronic device, metal foil with carrier and manufacturing method of printed wiring board
JP6176948B2 (en) Copper foil with carrier, method for producing copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board
JP6329731B2 (en) Copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board
JP6329727B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6336142B2 (en) Copper foil with carrier, method for producing copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

Address after: No.4, 10-fan, erdingmu, huzhimen, Tokyo, Japan

Patentee after: JX Nippon Mining & Metals Corp.

Address before: Tokyo, Japan

Patentee before: JX Nippon Mining & Metals Corp.