CN105392297B - Preparation method, the preparation method of copper-cover laminated plate, the preparation method of printing distributing board, the preparation method of e-machine and their product of Copper foil with carrier - Google Patents

Preparation method, the preparation method of copper-cover laminated plate, the preparation method of printing distributing board, the preparation method of e-machine and their product of Copper foil with carrier Download PDF

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Publication number
CN105392297B
CN105392297B CN201510535361.0A CN201510535361A CN105392297B CN 105392297 B CN105392297 B CN 105392297B CN 201510535361 A CN201510535361 A CN 201510535361A CN 105392297 B CN105392297 B CN 105392297B
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carrier
mentioned
copper foil
layer
copper
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CN105392297A (en
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森山晃正
永浦友太
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0147—Carriers and holders
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
    • H05K2203/0264—Peeling insulating layer, e.g. foil, or separating mask
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating

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

Abstract

The present invention provides a kind of manufacturing method of Copper foil with carrier, it includes following heat treatment steps: to sequentially have carrier, middle layer, very thin layers of copper, comprising silane coupling process layer surface-treated layer Copper foil with carrier, the heat treatment that the heating temperature carried out 1 hour~8 hours is 100 DEG C~220 DEG C, 1 hour~6 hours heating temperatures be 100 DEG C~220 DEG C heat treatment or 2 hours~4 hours heating temperatures be 160 DEG C~220 DEG C heat treatment.

Description

The preparation method of Copper foil with carrier, the preparation method of copper-cover laminated plate, the preparation method of printing distributing board, The preparation method of e-machine and their product
Technical field
The present invention relates to a kind of manufacturing method of Copper foil with carrier, the manufacturing method of copper-cover laminated plate, printing distributing boards Manufacturing method and the manufacturing method of e-machine, Copper foil with carrier, laminate, printing distributing board and e-machine.
Background technique
Printing distributing board is usually manufactured through following step: making insulating substrate and copper foil that copper-cover laminated plate then be made Later, conductive pattern is formed in copper-clad surface by etching.With the miniaturization of e-machine in recent years, high performance demand Increase and expand and carry the high density structure dressization of part or the high frequency of signal, to require printing distributing board have conductive pattern Imperceptibility (thin space) or high frequency answer equity.
It is corresponding with thin spaceization, require recently thickness 9 μm or less, even thickness is in 5 μm of copper foils below, so And this its mechanical strength of very thin copper foil is low, it is easily rupturable in the manufacture of printing distributing board or generate fold, therefore develop By the metal foil with thickness be used as carrier and across peeling layer very thin layers of copper is electrodeposited in thereon made of appendix body copper Foil.After the surface of very thin layers of copper is fitted in insulating substrate and is thermally compressed, carrier is removed via peeling layer and is removed.? After forming circuit pattern by resist in the very thin layers of copper exposed, etched using Sulfuric-acid-hydrogen-peroxide system etching solution Very thin layers of copper is removed, subtle electricity is formed by this gimmick (MSAP:Modified-Semi-Additive-Process) Road.
Herein, for becoming the very thin copper of surface major requirement with the very thin layers of copper of the Copper foil with carrier of the commissure of resin The peel strength of layer and resin base material is sufficient, and this peel strength is in high-temperature heating, wet processed, welding, Chemical treatment Abundance is also remained Deng after.The method for improving the peel strength between very thin layers of copper and resin base material, it is however generally that be with following Method is representative: in the very thin layers of copper after making a large amount of roughening particle be attached to profile (the concave-convex, coarse) increase on surface.
However, even in printing distributing board, if having partly leading for the needs for forming especially subtle circuit pattern The body package substrate very thin layers of copper big using this profile (concave-convex, coarse), then can remain unwanted copper in circuit etch Particle, can defective insulation between generation circuit pattern the problems such as.
Therefore, it has attempted not apply using on the surface of very thin layers of copper in No. WO2004/005588 (patent document 1) thick Change the Copper foil with carrier of processing as the Copper foil with carrier for fine circuits headed by conductor package substrate.Since its is low Adaptation (the removing of the influence of profile (bumps, roughness, coarse), this very thin layers of copper for not applying roughening treatment and resin Intensity) compared with general copper foil for printed wiring board, have the tendency that reduction.It is therefore desirable to make to Copper foil with carrier further Improvement.
Therefore, in Japanese Unexamined Patent Publication 2007-007937 bulletin (patent document 2) and Japanese Unexamined Patent Publication 2010-006071 In bulletin (patent document 3), record in the face of appendix body ultrathin copper foil contacted with polyimides system resins substrate (then), Ni layer of setting and/or Ni alloy-layer, setting chromate coating, Cr layers of setting and/or Cr alloy-layer, be arranged Ni layers and chromate coating, Ni layers and Cr layers of setting.By the way that the grade surface-treated layers are arranged, polyimides system resins substrate is close with appendix body ultrathin copper foil Desired Bonding strength can be can be obtained without the degree (imperceptibility) of roughening treatment or reduction roughening treatment by closing intensity.This Outside, it also records using silane coupling agent and is surface-treated or is applied antirust treatment.
[patent document 1] No. WO2004/005588 number
[patent document 2] Japanese Unexamined Patent Publication 2007-007937 bulletin
[patent document 3] Japanese Unexamined Patent Publication 2010-006071 bulletin.
Summary of the invention
In the exploitation of Copper foil with carrier, ensure that the peel strength of very thin layers of copper and resin base material is regarded always up to now Attach most importance to.Therefore, the circuit formative of very thin layers of copper is not inquired into sufficiently yet, still there is improved space.
To very thin layers of copper formed circuit, usually in the following manner carry out: by very thin layers of copper lamination after resin base material Carrier is removed, then, in the state of being provided with the photoresist of specific pattern in very thin layers of copper, is carried out using specific etching solution Etching process, the layers of copper for the part that removal is not covered by photoresist.Later, by removing photoresist, production has desired conductor figure The circuit of case.
Herein, when being etched using specific etching solution, if very thin layers of copper is attached with the interface of resin base material Near-end point is poor for the wetability of etching solution, then the wetting range of etching solution is insufficient.In this respect, attached with the interface of resin base material Near-end branch, which generates, etches non-uniform part, and circuit linearity becomes bad.The present invention provides the circuit for very thin layers of copper The manufacturing method of the good Copper foil with carrier of formative.Also, providing the good Copper foil with carrier of wetability of etching solution.
The present invention completed based on above-mentioned opinion is a kind of manufacturing method of Copper foil with carrier in one aspect, It includes following heat treatment steps: to sequentially have carrier, middle layer, very thin layers of copper, comprising silane coupling process layer table The Copper foil with carrier of surface treatment layer, the heat treatment or 1 that the heating temperature carried out 1 hour~8 hours is 100 DEG C~220 DEG C are small When~6 hours heating temperatures be 100 DEG C~220 DEG C heat treatment or 2 hours~4 hours heating temperatures be 160 DEG C~ 220 DEG C of heat treatment.
The present invention is a kind of manufacturing method of Copper foil with carrier in another aspect, and it includes following heat treatment steps It is rapid:, will be until heating temperature be reached to sequentially having carrier, middle layer, very thin layers of copper, the Copper foil with carrier of surface-treated layer The heat treatment that the heating temperature that heating rate is set as carrying out 1 hour~8 hours more than 50 DEG C/h is 100 DEG C~220 DEG C, Or 1 hour~6 hours heating temperatures are for 100 DEG C~220 DEG C of heat treatment or 2 hours~4 hours heating temperatures 160 DEG C~220 DEG C of heat treatment.
In one embodiment, the above-mentioned heating in above-mentioned heat treatment is fast for the manufacturing method of Copper foil with carrier of the invention Degree is 200 DEG C/h or less.
The manufacturing method of Copper foil with carrier of the invention in another embodiment, in room temperature after above-mentioned heat treatment step The tensile strength of lower measured carrier is 300MPa or more.
The manufacturing method of Copper foil with carrier of the invention is in yet another embodiment, in above-mentioned heat treatment step, It is to be heated under non-reactive gas ambient.
The manufacturing method of Copper foil with carrier of the invention is in yet another embodiment, in above-mentioned heat treatment step, Heat in the state of being involved in Copper foil with carrier into metal hollow tube.
The manufacturing method of Copper foil with carrier of the invention is in yet another embodiment, in above-mentioned heat treatment step, By tension when Copper foil with carrier is involved in into metal hollow tube be set as 5~100kgf/m or 20~100kgf/m to Heated.
The manufacturing method of Copper foil with carrier of the invention is in yet another embodiment, in above-mentioned heat treatment step, In the state of being involved in Copper foil with carrier into metal hollow tube, on one side with the rotation of 0.01~600 rotation/hour speed Turn above-mentioned hollow tube to be heated on one side.
Appendix body of the manufacturing method of Copper foil with carrier of the invention in yet another embodiment, before above-mentioned heat treatment Copper foil further sequentially has middle layer, very thin layers of copper on the surface of above-mentioned carrier side.
Appendix body of the manufacturing method of Copper foil with carrier of the invention in yet another embodiment, before above-mentioned heat treatment Copper foil further has surface-treated layer on the surface of above-mentioned carrier side.
For the manufacturing method of Copper foil with carrier of the invention in yet another embodiment, above-mentioned surface-treated layer includes roughening Process layer.
The manufacturing method of Copper foil with carrier of the invention is roughening in above-mentioned surface-treated layer in yet another embodiment The surface of process layer further has to be selected to be made of refractory layer, antirust coat, chromating layer and silane coupling process layer One or more of group layer.
Appendix body of the manufacturing method of Copper foil with carrier of the invention in yet another embodiment, before above-mentioned heat treatment Copper foil has on the surface of above-mentioned very thin layers of copper selected from by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane One layer or more of layer in group composed by process layer is coupled as surface-treated layer.
Appendix body of the manufacturing method of Copper foil with carrier of the invention in yet another embodiment, before above-mentioned heat treatment Copper foil has resin layer on above-mentioned surface-treated layer.
The present invention is a kind of manufacturing method of copper-cover laminated plate in yet another aspect, and using has through the invention Copper foil with carrier obtained by method.
The present invention is a kind of manufacturing method of printing distributing board in yet another aspect, and using has through the invention Copper foil with carrier obtained by method.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
It is ready to pass through Copper foil with carrier prepared by method of the invention and insulating substrate；
By above-mentioned Copper foil with carrier and insulating substrate lamination；And
After by above-mentioned Copper foil with carrier and insulating substrate lamination, through the step of carrier of above-mentioned Copper foil with carrier is removed And copper-cover laminated plate is formed,
Thereafter, pass through semi-additive process, subtractive process, part addition process or improvement semi-additive process (Modified Semi Additive method forms circuit either in).
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
The above-mentioned very thin layers of copper side surface of the Copper foil with carrier prepared by by means of the present invention or above-mentioned carrier side Circuit forming surface；
In the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier or above-mentioned carrier side in a manner of burying foregoing circuit Surface forms resin layer；
Circuit is formed on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed；And
After removing above-mentioned carrier, above-mentioned very thin layers of copper or above-mentioned carrier are removed, thus makes to be formed in above-mentioned very thin layers of copper The circuit for being buried in above-mentioned resin layer of side surface or above-mentioned carrier side surface exposes.
The present invention is a kind of manufacturing method of e-machine in yet another aspect, uses the side having through the invention Printing distributing board obtained by method.
The present invention is a kind of Copper foil with carrier, is to be made by means of the present invention in yet another aspect.
The present invention is a kind of Copper foil with carrier in yet another aspect, sequentially have carrier, middle layer, very thin layers of copper, Surface-treated layer comprising silane coupling process layer, in the horizontal plane with the surface-treated layer of ultrathin copper foil side in mode above Place Copper foil with carrier (other than the person that has resin layer), 30 μ L, which are added dropwise, at a position using pipette has sulfuric acid 24 The etching solution of the composition of 15 weight % of weight %- hydrogen peroxide (remainder is water), after wiping etching solution after placing 30 seconds, The maximum gauge of the trace of etching solution and the difference of minimum diameter are 10mm or less.
The present invention is a kind of Copper foil with carrier in yet another aspect, sequentially have carrier, middle layer, very thin layers of copper, Surface-treated layer comprising silane coupling process layer, in the horizontal plane with the surface-treated layer of ultrathin copper foil side in mode above Place Copper foil with carrier (other than the person that has resin layer), 30 μ L, which are added dropwise, at a position using pipette has sulfuric acid 24 The etching solution of the composition of 15 weight % of weight %- hydrogen peroxide (remainder is water), after wiping etching solution after placing 30 seconds, The maximum gauge of the trace of etching solution is 25mm or more.
The present invention is a kind of Copper foil with carrier in yet another aspect, sequentially have carrier, middle layer, very thin layers of copper, Surface-treated layer (is removed in mode above to place Copper foil with carrier with the surface-treated layer of ultrathin copper foil side in the horizontal plane Other than the person that has resin layer), 30 μ L, which are added dropwise, at a position using pipette has sulfuric acid 24 weight %- hydrogen peroxide 15 The etching solution of the composition of weight % (remainder is water), after wiping etching solution after placing 30 seconds, the maximum of the trace of etching solution The difference of diameter and minimum diameter is 10mm or less.
The present invention is a kind of Copper foil with carrier in yet another aspect, sequentially have carrier, middle layer, very thin layers of copper, Surface-treated layer (is removed in mode above to place Copper foil with carrier with the surface-treated layer of ultrathin copper foil side in the horizontal plane Other than the person that has resin layer), 30 μ L, which are added dropwise, at a position using pipette has sulfuric acid 24 weight %- hydrogen peroxide 15 The etching solution of the composition of weight % (remainder is water), after wiping etching solution after placing 30 seconds, the maximum of the trace of etching solution Diameter is 25mm or more.
Copper foil with carrier of the invention is in yet another aspect, the maximum gauge and minimum diameter of the trace of above-mentioned etching solution Difference be 5mm or less.
Copper foil with carrier of the invention in yet another aspect, the maximum gauge of the trace of above-mentioned etching solution be 35mm with On.
The present invention is a kind of laminate in yet another aspect, is made using Copper foil with carrier of the invention.
The present invention is a kind of laminate in yet another aspect, above-mentioned containing Copper foil with carrier and resin of the invention Part or all of the end face of Copper foil with carrier is covered by above-mentioned resin.
The present invention is a kind of laminate in yet another aspect, is by a Copper foil with carrier of the invention from above-mentioned The above-mentioned carrier side or above-mentioned surface of carrier side or above-mentioned surface-treated layer side laminated on another Copper foil with carrier of the invention Process layer side forms.
Laminate of the invention in one embodiment, the above-mentioned carrier side surface or above-mentioned of said one Copper foil with carrier The above-mentioned carrier side surface or above-mentioned surface-treated layer side surface of surface-treated layer side surface and another above-mentioned Copper foil with carrier Optionally it is configured via the direct lamination of solid.
Laminate of the invention in another embodiment, the above-mentioned carrier of said one Copper foil with carrier or above-mentioned surface Process layer is engaged with the above-mentioned carrier of another above-mentioned Copper foil with carrier or above-mentioned surface-treated layer.
Laminate of the invention is in yet another embodiment, and part or all of the end face of above-mentioned laminate is by resin Covering.
The present invention is a kind of printing distributing board in yet another aspect, is manufactured using Copper foil with carrier of the invention Made of.
The present invention is a kind of e-machine in yet another aspect, be using printing distributing board manufacture of the invention and At.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；And
After by above-mentioned Copper foil with carrier and insulating substrate lamination, through the step of carrier of above-mentioned Copper foil with carrier is removed And copper-cover laminated plate is formed,
Thereafter, electricity is formed by method either in semi-additive process, subtractive process, part addition process or improvement semi-additive process Road.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
In the above-mentioned very thin layers of copper side surface of Copper foil with carrier of the invention or above-mentioned carrier side circuit forming surface；
In the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier or above-mentioned carrier side in a manner of burying foregoing circuit Surface forms resin layer；
After forming above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed；And
After removing above-mentioned carrier or above-mentioned very thin layers of copper, above-mentioned very thin layers of copper or above-mentioned carrier are removed, thus makes to be formed The circuit for being buried in above-mentioned resin layer in above-mentioned very thin layers of copper side surface or above-mentioned carrier side surface exposes.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
In the above-mentioned very thin layers of copper side surface of Copper foil with carrier of the invention or above-mentioned carrier side circuit forming surface；
In the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier or above-mentioned carrier side in a manner of burying foregoing circuit Surface forms resin layer；
Circuit is formed on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed；And
After removing above-mentioned carrier or above-mentioned very thin layers of copper, above-mentioned very thin layers of copper or above-mentioned carrier are removed, thus makes to be formed The circuit for being buried in above-mentioned resin layer in above-mentioned very thin layers of copper side surface or above-mentioned carrier side surface exposes.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
By the above-mentioned very thin layers of copper side surface of Copper foil with carrier of the invention or above-mentioned carrier side surface and resin substrate into Row lamination；
The lamination with above-mentioned Copper foil with carrier have resin substrate side be opposite side above-mentioned very thin layers of copper side surface or This two layers of 1 resin layer and circuit is at least arranged in above-mentioned carrier side surface；And
After forming this two layers of above-mentioned resin layer and circuit, above-mentioned carrier or above-mentioned very thin is removed from above-mentioned Copper foil with carrier Layers of copper.
The present invention is a kind of manufacturing method of printing distributing board, it includes following steps in yet another aspect:
The above-mentioned carrier side surface of Copper foil with carrier of the invention and resin substrate are subjected to lamination；
There is the side of resin substrate at least to set for the very thin layers of copper side surface of opposite side in the lamination with above-mentioned Copper foil with carrier Set this two layers of 1 resin layer and circuit；And
After forming this two layers of above-mentioned resin layer and circuit, above-mentioned very thin layers of copper is removed from above-mentioned Copper foil with carrier.
Through the invention, it is possible to provide a kind of manufacturer of the good Copper foil with carrier of circuit formative to very thin layers of copper Method.Also, providing the good Copper foil with carrier of wetability of etching solution.
Detailed description of the invention
Figure 1A~Fig. 1 C is the specific implementation for having used the manufacturing method of printing distributing board of Copper foil with carrier of the invention Example until the exposure-development to circuit plating-removal photoresist the step of in distributing board section schematic diagram.
Fig. 2 D~Fig. 2 F is the specific implementation for having used the manufacturing method of printing distributing board of Copper foil with carrier of the invention Example until the laminated resin and the 2nd layer of Copper foil with carrier to laser aperture the step of in distributing board section schematic diagram.
Fig. 3 G~Fig. 3 I is the specific implementation for having used the manufacturing method of printing distributing board of Copper foil with carrier of the invention The schematic diagram of distributing board section in the step of self-forming through-hole filler of example is until removing the 1st layer of carrier.
Fig. 4 J~Fig. 4 K is the specific implementation for having used the manufacturing method of printing distributing board of Copper foil with carrier of the invention Example from fast-etching until forming convex block-copper post the step of in distributing board section schematic diagram.
Fig. 5: being the overlook view photo of circuit, indicate experimental example in observed from above circuit obtained from electricity The measuring method of the difference (μm) of the maxima and minima of road lower end width.
Specific embodiment
The manufacturing method > of < Copper foil with carrier
As sequentially having carrier, middle layer, the use form of the Copper foil with carrier of very thin layers of copper, firstly, by very thin After the surface of layers of copper fits in insulating substrate and is thermally compressed, carrier is removed.Then, with insulating substrate then very thin The photoresist of layers of copper setting specific pattern.Then, it is etched using specific etching solution, is not covered by photoresist by removal The very thin layers of copper of the part of lid, and conductive pattern as a purpose is formed, for example, production has the printing distributing board of particular electrical circuit Deng.Herein, by specific etching solution come when being etched, if part near the interface with resin base material of very thin layers of copper Poor for the wetability of etching solution, then the wetting range of etching solution becomes insufficient.When in this respect, at the interface with resin base material Nearby part can generate the non-uniform part of etching, and circuit linearity is made to become bad.
In this regard, the manufacturing method of Copper foil with carrier of the invention is in one aspect, it is to prepare sequentially have carrier, centre Layer, very thin layers of copper, comprising silane coupling process layer surface-treated layer Copper foil with carrier after, to the Copper foil with carrier carry out 1 Hour~8 hours heating temperatures be 100 DEG C~220 DEG C heat treatment.Furthermore above-mentioned 100 DEG C~220 DEG C are to indicate to heat Environment temperature in device.In this way, the heat treatment for being 100 DEG C~220 DEG C by the heating temperature carried out 1 hour~8 hours, Since the unreacted hydrogen-based in silane coupling process layer will do it dehydration condensation, the process layer is in addition to that can become more It securely improves except the adaptation with resin base material, can also make near the interface between very thin layers of copper and surface-treated layer, and Atom composition discontinuous section near interface when with the situation of multiple-level surface process layer between the multilayer passes through mutual It spreads and is formed as continuous atom composition distribution, therefore partially for etching near the interface with resin base material of very thin layers of copper The wetability of liquid becomes well, and partially etching is uniform near the interface with resin base material, and makes the circuit straight line of very thin layers of copper Property becomes good.Furthermore for typical, very thin layers of copper is mainly made of copper.Also, surface-treated layer can also sequentially have at roughening It manages layer and/or refractory layer and/or antirust coat and/or chromating layer and silane is coupled process layer, it can also be in any order To have these layers.Roughening treatment layer is preferably mainly made of alloy, such as copper alloy or nickel alloy or cobalt alloy etc..Roughening Process layer can also be mainly made of copper.Chromating layer is preferably mainly made of metal oxide.Silane is coupled process layer Preferably it is made of organo-silicon compound.
Generally, due to carried out when being bonded Copper foil with carrier with resin base material 50~120 minutes or so temperature be 160~ 220 DEG C of heating crimping, thus while phase counterdiffusion above-mentioned at this moment can also carry out to a certain extent, but regards condition Have the insufficient situation of phase counterdiffusion.Therefore, by by above-mentioned heat treatment with resin base material then before carry out, can make to etch The improvement effect of property and its uniformity is more certain.
Furthermore when the very thin layers of copper side surface of Copper foil with carrier detects the situation of Si, the surface analyses such as XPS can be passed through To judge that there are silane to be coupled process layer.
In the heat treatment, in temperature not up to 100 DEG C or heating time not up to 1 hour situation when, between treated layers Interface near phase counterdiffusion become insufficient.Also, in the heat treatment, it is more than 220 DEG C in temperature or heating time is more than When 8 hours situations, it can be possible to generate carrier and the peel strength of ultrathin copper foil generates variation, or the crystalline substance of very thin layers of copper occurs Grain growth to make mechanical strength decline etc. other the problem of.In the heat treatment step, it is small preferably to carry out 1 hour~6 When heating temperature be 100 DEG C~220 DEG C of heat treatment, the heating temperature preferably carried out 1 hour~6 hours is 120 DEG C ~220 DEG C of heat treatment, the heat treatment that the heating temperature more preferably carried out 2 hours~4 hours is 160 DEG C~220 DEG C.
The manufacturing method of Copper foil with carrier of the invention includes following heat treatment steps: to sequentially in another aspect Have carrier, middle layer, very thin layers of copper, the Copper foil with carrier of surface-treated layer, by the heating rate until arrival heating temperature The heat treatment that the heating temperature for being set as carrying out 1 hour~8 hours more than 50 DEG C/h is 100 DEG C~220 DEG C.Herein, should Heating rate is the heating rate since heating until first time reaches heating temperature.It is 50 DEG C/h in heating rate Situation below has the case where productivity of heat treatment declines, in addition, since the time of heat treatment is long, there is appendix body The case where copper foil surface is oxidized.Also, heating rate is preferably 200 DEG C/h or less.It is more than 200 DEG C/h in heating rate Situation, have and cause elongation degree different because of the difference of the coefficient of thermal expansion between core and Copper foil with carrier, to generate The situation of fold.Also, having the feelings of wetability deterioration of the Copper foil with carrier for etching solution in the situation more than 200 DEG C/h Shape.Its reason is not known, it is possible that tempestuously expanding because of due to Copper foil with carrier, contact when leading to be rolled into coiled type Surface-treated layer and carrier between friction or offset occurs, or generate and the stress of surface-treated layer concentrated, the friction/partially The generation of the displacement of medium and in surface-treated layer the part of shifting/stress collection is related, which can be to surface-treated layer The disperse state of element impacts.
Heating rate until above-mentioned arrival heating temperature is more preferably 70 DEG C/h~200 DEG C/h, even more preferably It is 100 DEG C/h~200 DEG C/h, still more preferably from 150 DEG C/h~200 DEG C/h.
In the manufacturing method of Copper foil with carrier of the invention, in the heat treatment step, preferably meeting is not being contained It causes to be heated in the environment of carrier surface and the gases such as very thin layers of copper surface oxidation or oxygen, the vapor of deterioration, example Such as preferably helium, neon, argon, nitrogen and this etc. mixed gas non-reactive gas ambient under heated.
In the manufacturing method of Copper foil with carrier of the invention, in above-mentioned heat treatment step, preferably by appendix body Copper foil is heated in the state of being involved in into metal hollow tube.By being involved in by Copper foil with carrier to made of metal Hollow tube in the state of heated, can utilize ventilate in thermally conductive good metal tube and also from inside come pair Copper foil with carrier is heated, so as to be effectively heat-treated.Metal hollow tube is not particularly limited, such as preferably For carbon steel, stainless steel, as its size, can be set as outer diameter is 7cm~20cm and with a thickness of 0.5cm~3.0cm.
In the manufacturing method of Copper foil with carrier of the invention, in above-mentioned heat treatment step, preferably carry out following Heat treatment: tension when Copper foil with carrier is involved in metal hollow tube is set as 5~100kgf/m.The tension is attached The tension of the per unit width (width 1m) of carrier copper foil.By the way that the tension is set as 5kgf/m or more, being involved in for oxygen can inhibit To prevent the oxidation of Copper foil with carrier.Also, by the tension is set as 100kgf/m hereinafter, when can prevent from batching it is generated Fold.
The tension is more preferably 10kgf/m or more, more preferably 20kgf/m or more, more preferably 20~100kgf/m, then More preferably 20~50kgf/m, still more preferably from 20~30kgf/m.
In the manufacturing method of Copper foil with carrier of the invention, in above-mentioned heat treatment step, preferably by appendix In the state that body copper foil is involved in into metal hollow tube, on one side among the above with the rotation of 0.01~600 rotation/hour speed Blank pipe is heated on one side.By the way that one side is with 0.01 rotation/more than hour and 600 rotations/hour is below relatively low Speed carry out rotating hollow tube, heated on one side, can remove and be involved in oxygen between copper foil and copper foil through batching, To prevent the oxidation of the Copper foil with carrier in heat treatment.The rotation speed of the hollow tube be more preferably 0.01~180 rotation/ Hour, more preferably 0.01~120 rotation/hour, more preferably 0.01~70 rotation/hour, more preferably 1~70 rotation/ Hour.
In the manufacturing method of Copper foil with carrier of the invention, surveyed at normal temperature after preferably above-mentioned heat treatment step The tensile strength of the carrier obtained is 300MPa or more.Pass through load measured at normal temperature after heat treatment step as described above The tensile strength of body is 300MPa or more, rigidity when very thin layers of copper can sufficiently be kept to play the function as carrier.
The tensile strength of the carrier is more preferably 350MPa or more, still more preferably from 380MPa or more, more typically 350~ 500MPa, then more typically 380~450MPa.
< Copper foil with carrier >
Hereinafter, the embodiment of Copper foil with carrier is said to before heat treatment of the invention if not specified It is bright, but the embodiment is for (appendix prepared by the manufacturing method of Copper foil with carrier through the invention after heat treatment Body copper foil) it is equally applicable.
Copper foil with carrier of the invention sequentially has carrier, middle layer, very thin layers of copper, surface-treated layer.Copper foil with carrier The application method of itself is that such as the surface of very thin layers of copper can be fitted in paper base material phenol resin, paper base material ring well known to dealer Oxygen resin, synthetic fibers cloth base material epoxy resin, glass cloth-paper composite base material epoxy resin, glass cloth-glass nonwoven fabric are multiple Close substrate epoxy resin and glass cloth base material epoxy resin, polyester film, polyimide film, liquid crystalline polymer film, fluororesin film etc. Insulating substrate simultaneously removes carrier after being thermally compressed, and the very thin layers of copper for being bonded in insulating substrate is etched into the conductor figure of target Case finally manufactures printing distributing board.
< carrier >
Can be used for carrier of the invention it is typical for for metal foil or resin film, such as with copper foil, copper alloy foil, nickel Foil, nickel alloy foil, iron foil, ferroalloy foil, stainless steel foil, aluminium foil, alloy foil, insulating resin film, polyimide film, LCP film Form provide.
It can be used for providing in the form of rolled copper foil or electrolytic copper foil for carrier of the invention is typical.In general, electrolysis Copper foil is to precipitate into copper on the rotating cylinder of titanium or stainless steel from copper sulfate bath electrolysis and manufacture, and rolled copper foil is that benefit is repeated It is manufactured with the plastic processing and heat treatment of stack.As the material of copper foil, in addition to refined copper (JIS H3100 alloy number C1100) or other than the high-purity coppers such as oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), Such as the copper alloy also can be used and mix Sn copper, mix Ag copper, be added to Cr, Zr or Mg etc., the inferior system of card for being added to Ni and Si etc. The copper alloy of copper alloy etc.
In addition, can use following electrolyte composition and manufacturing condition production as electrolytic copper foil.
Furthermore made in plating of the manufacture of documented copper foil, the surface treatment of copper foil or copper foil etc. in this specification The remainder for the treatment of fluid is then water as long as no especially expressing.
< electrolyte forms >
Copper: 90~110g/L
Sulfuric acid: 90~110g/L
Chlorine: 50~100ppm
It levels agent 1 (bis- (3- sulfopropyl) disulphide): 10~30ppm
It levels agent 2 (amine compounds): 10~30ppm
The amine compounds of following below formula can be used in above-mentioned amine compounds.
(in the chemical formula, R1And R2Selected from by hydroxy alkyl, ether, aryl, aromatic series replace alkyl, unsaturated alkyl, The group of alkyl composition)
< manufacturing condition >
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 " being used alone in this specification, also including copper alloy foil.
About the thickness that can be used for carrier of the invention it is not also specifically limited, as long as appropriate adjustment is in performance conduct The suitable thickness of aspect institute of the effect of carrier, such as can be set to 5 μm or more.If but it is blocked up, increased production cost, It is generally preferred that being set as 35 μm or less.Therefore, it is 8~70 μm for the thickness of carrier is typical, is 12~70 μ for more typical M is 18~35 μm for more typical.In addition, the small thickness of carrier is preferred for the viewpoint for reducing cost of material.Therefore, Be for the thickness of carrier is typical 5 μm or more and 35 μm hereinafter, preferably 5 μm or more and 18 μm hereinafter, preferably 5 μm or more and 12 μm hereinafter, preferably 5 μm or more and 11 μm hereinafter, preferably 5 μm or more and 10 μm or less.In addition, small in carrier thickness In the case of, gauffer is easy to produce when carrier leads to foil.Gauffer is generated in order to prevent, effectively for example manufactures Copper foil with carrier The transport roller of device is smooth, or shortens the distance of transport roller and next transport roller.In addition, in the manufacture as printing distributing board In the case that the implantation (Enbedded Process) of one of method uses Copper foil with carrier, the rigidity of carrier is necessary for high. Therefore, in the case where being used for implantation, the thickness of carrier is preferably 18 μm or more and 300 μm hereinafter, preferably 25 μm or more And 150 μm hereinafter, preferably 35 μm or more and 100 μm hereinafter, even more preferably be 35 μm or more and 70 μm or less.
< middle layer >
Middle layer is set on carrier.Other layers can also be set between carrier and middle layer.In used in the present invention Interbed is not particularly limited as long as being constructed as follows: very thin layers of copper is not the step of Copper foil with carrier is to insulating substrate lamination before It is easily removed from carrier, on the other hand, very thin layers of copper can be removed from carrier after the step of to insulating substrate lamination.For example, this hair The middle layer of bright Copper foil with carrier contains selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these metals One or more of alloy, the hydrate of these metals, the oxide of these metals, group composed by organic matter.Also, Middle layer can also be multilayer.Also, middle layer may also be arranged on the two sides of carrier.
Also, for example, middle layer can be constituted in the following way: from carrier side formed by selected from by Cr, Ni, Co, Fe, Mo, One of groups of elements element composed by Ti, W, P, Cu, Al, Zn constitute single metal layer, or by selected from by Cr, Ni, The alloy-layer that the element of one or more of groups of elements composed by Co, Fe, Mo, Ti, W, P, Cu, Al, Zn is constituted, It is formed thereon by being constituted selected from one of groups of elements element composed by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Single metal layer, or as be selected from one of groups of elements as composed by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn Or the alloy-layer that two or more elements is constituted, or be made of by being selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn One or more of groups of elements element hydrate or the layer that is constituted of oxide or organic matter.
Also, the middle layer containing Ni can be arranged on the single or double of carrier.Middle layer is preferably sequentially accumulated on carrier Layer nickel or nickeliferous alloy wantonly a kind of layer and containing chromium, evanohm, chromium oxide in wantonly a kind or more of layer and structure At.Also, preferably nickel or nickeliferous alloy wantonly a kind of layer and/or containing chromium, evanohm, chromium oxide in wantonly 1 Kind or more layer in contain zinc.Herein, so-called nickeliferous alloy, refer to by nickel with selected from by cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, The alloy that one or more of group composed by aluminium, phosphorus, tungsten, tin, arsenic and titanium element is constituted.Nickeliferous alloy can also be for by 3 kinds The alloy that above element is constituted.Also, so-called evanohm, refer to by chromium with selected from by cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, The alloy that one or more of group composed by phosphorus, tungsten, tin, arsenic and titanium element is constituted.Evanohm can also be for by 3 kinds or more of member The alloy that element is constituted.Also, containing chromium, evanohm, chromium oxide in wantonly a kind or more of layer can also be chromating layer. Herein, so-called chromating layer refers to through the liquid processing containing chromic anhybride, chromic acid, two chromic acid, chromate or two chromate Layer.Chromating layer can also (also be gold containing elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titaniums Any form such as category, alloy, oxide, nitride, sulfide).As the specific embodiment of chromating layer, can arrange It lifts: pure chromating layer or zinc chromate process layer etc..In the present invention, by through chromic anhybride or two chromic acid aqueous solutions of potassium processing Chromating layer is known as pure chromating layer.Also, in the present invention, the place containing chromic anhybride or two potassium chromates and zinc will be passed through The chromating layer of reason liquid processing is known as zinc chromate process layer.
Also, middle layer preferably on carrier sequentially lamination nickel, nickel-zinc alloy, nickel-phosphor alloy, in nickel-cobalt alloy Wantonly a kind of layer and zinc chromate process layer, pure chromating layer, wantonly a kind of the layer in chrome layer and constitute, middle layer into And preferably on carrier sequentially lamination nickel layer or nickel-zinc alloy-layer and zinc chromate process layer and constitute, or sequentially lamination Nickel-zinc alloy-layer and pure chromating layer or zinc chromate process layer and constitute.The adhesion of nickel and copper is higher than chromium and copper Adhesion, therefore when removing very thin layers of copper, become the interface peel in very thin layers of copper and chromating layer.Also, in The nickel of interbed expects the barrier effect for preventing copper component from diffusing to very thin layers of copper from carrier.Also, preferably misaligning interbed progress Chromium plating and form chromating layer.Chromium plating is fine and close chromium oxide layer to be formed on surface, therefore forming pole using plating When thin copper foil, resistance rises, and is easy to produce pin hole.The surface for being formed with chromating layer is to be formed with compared with chromium plating not Fine and close chromium oxide layer, therefore it is not easy to become resistance when forming ultrathin copper foil using plating, and pin hole can be reduced.Herein, By forming zinc chromate process layer as chromating layer, and make resistance when forming ultrathin copper foil using plating lower than usual Chromating layer, the generation of pin hole can be further suppressed.
When using situation of the electrolytic copper foil as carrier, for reducing the viewpoint of pin hole, preferably set in glassy surface Set middle layer.
When chromating layer in middle layer is present in the interface of very thin layers of copper compared with unfertile land, accumulated to insulating substrate Very thin layers of copper will not be removed from carrier before the step of layer, on the other hand, can get after the step of carrying out lamination to insulating substrate The characteristic that very thin layers of copper can be removed from carrier, so it is preferred that.In not set nickel layer or nickeliferous alloy-layer, (such as nickel-zinc is closed Layer gold) and when the situation of the boundary that makes chromating layer be present in carrier and very thin layers of copper, fissility does not almost improve, in nothing Chromating layer and directly by the situation of nickel layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) and very thin layers of copper lamination When, as the nickel amount peel strength in nickel layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) is too strong or excessively weak, and can not Obtain peel strength appropriate.
Also, if chromating layer is present in the friendship of carrier and nickel layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) Boundary, then when removing very thin layers of copper, middle layer is also removed therewith, i.e., peeling-off between carrier and middle layer, so it is not good enough. Such situation can not only occur in the case where chromating layer is arranged with the interface of carrier, if at the interface with very thin layers of copper Chromium content is excessive when chromating layer is arranged, then can also occur.Think the reason is that since copper and nickel are easy solid solution, so If contacting the grade, adhesion can be improved because of phase counterdiffusion, become to be not easily stripped, on the other hand, since chromium and copper are not easy Solid solution, is not susceptible to phase counterdiffusion, so the interface adhesion in chromium and copper is weaker, is easily peeled off.Also, in the nickel amount of middle layer When insufficient situation, micro chromium is only deposited between carrier and very thin layers of copper, so the two carries out closely sealed and becomes difficult to remove.
The nickel layer of middle layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) can for example pass through such as plating, electroless plating Apply and dipping plating wet type plating, or as sputter, CVD and PDV dry type plating and formed.It is excellent for the viewpoint of cost It is selected as being electroplated.It, can be by the dry type plating of such as CVD and PDV or such as electroless plating furthermore when carrier is the situation of resin film And it impregnates the wet type plating of plating and forms middle layer.
Also, chromating layer can for example be formed by electrolytic chromate or dipping chromate etc., but dense since chromium can be improved Degree, becomes very thin layers of copper well from the peel strength of carrier, so preferably formed by electrolytic chromate.
The middle layer of Copper foil with carrier of the invention can also on carrier sequentially lamination nickel layer, and organise containing nitrogenous It closes object, the organic compound of sulfur-bearing and the organic matter layer of any one of carboxylic acid and constitutes.Also, Copper foil with carrier of the invention Middle layer can also sequentially lamination contains nitrogenous organic compound, the organic compound of sulfur-bearing and any in carboxylic acid on carrier The organic matter layer and nickel layer of person and constitute.Also, containing the organic compound and carboxylic of nitrogenous organic compound, sulfur-bearing as this The organic matter of any one of acid can enumerate BTA (benzotriazole), MBT (mercaptobenzothiazoler) etc..
Also, as organic matter contained by middle layer, it is preferable to use by selected from nitrogenous organic compound, sulfur-bearing it is organic One kind or two or more constitutor in compound and carboxylic acid.In nitrogenous organic compound, the organic compound and carboxylic acid of sulfur-bearing Among, nitrogenous organic compound includes the nitrogenous organic compound with substituent group.It organises as specifically nitrogenous Close object, it is preferable to use triazole compounds i.e. 1 with substituent group, 2,3- benzotriazole, carboxyl benzotriazole, N', N'- are bis- (benzotriazole ylmethyl) urea, 1H-1,2,4- triazole and 3- amido -1H-1,2,4- triazole etc..
The organic compound of sulfur-bearing preferably use mercaptobenzothiazoler, Vencide, trithiocyanuric acid and 2- benzimidazole mercaptan etc..
As carboxylic acid, monocarboxylic acid is especially preferably used, wherein preferably using oleic acid, linolenic acid and linolenic acid Deng.
Above-mentioned organic matter preferably contain with a thickness of 25nm or more and 80nm hereinafter, more preferably containing 30nm or more and 70nm or less.Middle layer can also contain there are many (more than one) above-mentioned organic matter.
Furthermore the thickness of organic matter can be carried out as follows measurement.
The organic matter thickness G T.GT.GT of < middle layer
By the very thin layers of copper of Copper foil with carrier from after carrier removing, to the middle layer side surface of the very thin layers of copper of exposing, XPS measurement is carried out with the middle layer side surface of the carrier of exposing, and depth profile is made.It then, can will be from very thin layers of copper Middle layer side surface initially becomes 3at% depth below to concentration of carbon and is set as A (nm), by from the middle layer side surface of carrier extremely Concentration of carbon initially becomes 3at% depth below and is set as B (nm), by the thickness of total organic matter for being set as middle layer of A and B (nm)。
The operating condition of XPS is shown in following.
Device: XPS measurement device (ULVAC-PHI company, model 5600MC)
Ultimate vacuum: 3.8 × 10- 7Pa
X-ray: monochromatic AlK α or polyenergetic MgK α, X-ray output 300W, 800 μm of φ of area of detection, sample and detection 45 ° of device angulation
Ion beam: ionic species Ar+, acceleration voltage 3kV, scan area 3mm × 3mm, sputtering rate 2.8nm/min (SiO2Conversion)
The application method of the organic matter contained by middle layer is carried out below for the method for forming middle layer in carrier foils It describes and illustrates.It is that above-mentioned organic matter is dissolved in solvent and makes carrier impregnation in the solvent that middle layer is formed on carrier In, or can the face for middle layer to be formed carried out using shower method, spray-on process, dropping method and electrodeposition process etc., be not necessarily to Using the method being particularly limited to.At this point, the concentration of the organic solvent in solvent is in above-mentioned whole organic matters, preferably concentration 0.01g/L~30g/L, 20~60 DEG C of liquid temperature of range.The concentration of organic matter is not particularly limited, and script concentration is higher or lower Equal no problem.Furthermore there are following tendencies: the concentration of organic matter is higher, in addition, carrier connects to the solvent for dissolving above-mentioned organic matter The touching time is longer, and the organic matter thickness of middle layer is bigger.Also, in the thicker situation of the organic matter thickness of middle layer, there is suppression The effect bigger tendency for the organic matter that Ni processed is spread to very thin layers of copper side.
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 middle layer and very thin layers of copper.Very thin layers of copper It can be formed by the plating of the electrobath using copper sulphate, cupric pyrophosphate, amidosulfonic acid copper, copper cyanider etc., so that it may in high electricity It is formed under current density for the aspect of layers of copper, preferably copper sulphate is bathed.There is no particular restriction for the thickness of very thin layers of copper, is usually thinner than Carrier, for example, 12 μm or less.0.5~12 μm, more typically 1~5 μm, and then more typically 1.5~5 μm are typically, in turn More typically 2~5 μm.Furthermore very thin layers of copper may also be arranged on the two sides of carrier.
< roughening treatment and other surface treatment >
It can be by for example making to implement roughening ands well grade with the adaptation of insulating substrate on the surface of very thin layers of copper Processing, so that roughening treatment layer be arranged.Roughening treatment can for example be carried out and forming roughening particle using copper or copper alloy. Roughening treatment can also be fine.Roughening treatment layer, which can be, to be made of by being selected from copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc Group in any simple substance or the layer etc. that is constituted containing any above alloy.Also, forming roughening using copper or copper alloy After particle, offspring or three times particle further can also be configured using nickel, cobalt, copper, the simple substance of zinc or alloy etc. Roughening treatment.Then, nickel, cobalt, copper, the simple substance of zinc or alloy etc. also be can use and form refractory layer and/or antirust coat, it can also be into One step implements the processing such as chromic acid salt treatment, silane coupling processing on its surface.Or it can also be utilized without roughening treatment Nickel, cobalt, copper, the simple substance of zinc or alloy etc. form refractory layer or antirust coat, further implement chromic acid salt treatment, silane on its surface The processing such as coupling processing.That is, can be formed on the surface of roughening treatment layer selected from by refractory layer, antirust coat, chromate The layer of one or more of group composed by process layer and silane coupling process layer, can also form on the surface of very thin layers of copper and select The layer of one or more of group composed by free refractory layer, antirust coat, chromating layer and silane coupling process layer.Again Person, above-mentioned refractory layer, antirust coat, chromating layer, silane coupling process layer can be formed respectively multilayer (such as 2 layers or more, 3 layers with first-class).So-called chromating layer herein can be above-mentioned chromating layer, can also be at other chromate Manage layer.
Furthermore above-mentioned silane is coupled process layer, in the manufacture of the Copper foil with carrier of the another aspect of above-mentioned the present application It is as described above necessary constitutive requirements, in addition, the manufacturer of the Copper foil with carrier of the another aspect of the present application in method Method is comprising following heat treatment step persons: for sequentially have carrier, middle layer, very thin layers of copper, surface-treated layer it is attached Heating rate until reaching heating temperature is set as more than 50 DEG C/h by carrier copper foil, is then carried out at 100 DEG C~220 DEG C Heat treatment in 1 hour~8 hours.
As refractory layer, antirust coat, well known refractory layer, antirust coat can be used.For example, refractory layer and/or antirust coat Can for containing selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, tantalum group in More than one element layer, can also for by selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, The metal layer or alloy-layer that the element of one or more of the group of silver, platinum family element, iron, tantalum is constituted.Also, refractory layer and/or anti- Rusty scale can also containing comprising selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminium, gold, silver, platinum family element, iron, Oxide, nitride, the silicide of the element of one or more of the group of tantalum.Also, refractory layer and/or antirust coat can also for containing The layer of nickel-zinc alloy.Also, refractory layer and/or antirust coat can also be nickel-zinc alloy-layer.Above-mentioned nickel-zinc alloy-layer can for except Other than inevitable impurity, contain nickel 50wt%~99wt%, zinc 50wt%~1wt% person.Above-mentioned nickel-zinc alloy-layer Total adhesion amount of zinc and nickel is 5~1000mg/m2, preferably 10~500mg/m2, preferably can also be 20~100mg/m2.Also, (the attachment of=nickel of the ratio between the nickel adhesion amount and amount of zinc adhesion of the above-mentioned layer containing nickel-zinc alloy or above-mentioned nickel-zinc alloy-layer Amount/zinc adhesion amount) it is preferably 1.5~10.Also, the nickel of the above-mentioned layer containing nickel-zinc alloy or above-mentioned nickel-zinc alloy-layer is attached Amount be preferably 0.5mg/m2~500mg/m2, more preferably 1mg/m2~50mg/m2.Refractory layer and/or antirust coat be containing When the situation of the layer of nickel-zinc alloy, the inner wall part and de-smear of through-hole (through hole) or via hole (viahole) etc. (desmear) interface of copper foil and resin substrate is difficult to by de-smear corrosion when liquid contacts, copper foil and resin substrate it is closely sealed Property can be promoted.
Such as it is 1mg/m that refractory layer and/or antirust coat, which can be by adhesion amount,2~100mg/m2, preferably 5mg/m2~ 50mg/m2Nickel or nickel alloy layer, with adhesion amount be 1mg/m2~80mg/m2, preferably 5mg/m2~40mg/m2Tin layers sequentially Lamination forms, and above-mentioned nickel alloy layer can also be made of any one of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt.Also, refractory layer And/or the nickel or nickel alloy and total adhesion amount of tin of antirust coat are preferably 2mg/m2~150mg/m2, more preferably 10mg/m2 ~70mg/m2.Also, refractory layer and/or antirust coat are preferably [the nickel adhesion amount in nickel or nickel alloy]/[tin adhesion amount]=0.25 ~10, more preferably 0.33~3.If Copper foil with carrier is processed into printing distributing board using the refractory layer and/or antirust coat Peel strength, chemical-resistant deterioration rate of the peel strength of later circuit etc. can become good.
Furthermore silane coupling, which handles used silane coupling agent, can be used well known silane coupling agent, such as can be used Amine system silane coupling agent or epoxy silane coupling agent, sulfydryl system silane coupling agent.Also, vinyl can also be used in silane coupling agent Trimethoxy silane, ethenylphenyl trimethoxy silane, γ-metacryloxy propyl trimethoxy silicane (γ-met Hacryloxypropyltrimethoxysilane), γ-glycidoxypropyltrime,hoxysilane (γ- Glycidoxypropyltrimethoxysilane), 4- glycidyl butyl trimethoxy silane, three second of γ-aminocarbonyl propyl Oxysilane, N- β (amido ethyl) γ-aminocarbonyl propyl trimethoxy silane, N-3- (4- (3- amido propoxyl group) fourth oxygen Base) propyl -3- aminocarbonyl propyl trimethoxy silane, imidizole silane, triazine silane, γ mercaptopropyitrimethoxy silane Deng.
Epoxy silane, amine system silane, metacryloxy system silane, sulfydryl can also be used in above-mentioned silane coupling process layer It is silane coupling agents such as silane etc. and is formed.Furthermore such silane coupling agent can also be use mixing two or more.Wherein, excellent It is selected as using amine system silane coupling agent or epoxy silane coupling agent institute former.
So-called amine system silane coupling agent can also be for selected from the group person as composed by following substance herein: N- (2- amido Ethyl) -3- aminocarbonyl propyl trimethoxy silane, 3- (N- styrylmethyl -2- amido ethyl amido) propyl front three Oxysilane, 3- aminocarbonyl propyl triethoxysilane, bis- (2- hydroxyethyl) -3- aminocarbonyl propyl triethoxysilanes, amine Base propyl trimethoxy silicane, N- methylamino propyl trimethoxy silicane, N- phenyl aminocarbonyl propyl trimethoxy silane, N- (3- propenyloxy group -2- hydroxypropyl) -3- aminocarbonyl propyl triethoxysilane, 4- amido butyl triethoxysilicane Alkane, (amido ethyl aminomethyl) phenethyl trimethoxy silane, N- (2- amido ethyl -3- aminocarbonyl propyl) trimethoxy Silane, N- (2- amido ethyl -3- aminocarbonyl propyl) three (2- ethyl hexyl oxy) silane, 6- (aminohexyl aminocarbonyl propyl) Trimethoxy silane, aminocarbonyl phenyl trimethoxy silane, 3- (1- amido propoxyl group) -3,3- dimethyl -1- acrylic Trimethoxy silane, 3- aminocarbonyl propyl three (methoxyethoxyethoxy) silane, 3- aminocarbonyl propyl triethoxysilane, 3- aminocarbonyl propyl trimethoxy silane, ω-amido undecyltrimethoxysilane, 3- (2-N- benzylamino ethylamine Base propyl) trimethoxy silane, bis- (2- hydroxyethyl) -3- aminocarbonyl propyl triethoxysilanes, (N, N- diethyl - 3- aminocarbonyl propyl) trimethoxy silane, (N, N- dimethyl -3- aminocarbonyl propyl) trimethoxy silane, N- methylamino third Base trimethoxy silane, N- phenyl aminocarbonyl propyl trimethoxy silane, 3- (N- styrylmethyl -2- amido ethylamine Base) propyl trimethoxy silicane, γ-aminocarbonyl propyl triethoxysilane, N- β (amido ethyl) γ-aminocarbonyl propyl trimethoxy Base silane, N-3- (4- (3- amido propoxyl group) butoxy) propyl -3- aminocarbonyl propyl trimethoxy silane.
Silane coupling process layer is more satisfactory to be set as 0.05mg/m to convert with silicon atom2~200mg/m2, preferably 0.15mg/m2~20mg/m2, preferably 0.3mg/m2~2.0mg/m2Range.In the situation of above range, substrate can be made The adaptation of resin and surface treatment copper foil is more promoted.
Also, can be to very thin layers of copper, roughening treatment layer, refractory layer, antirust coat, silane coupling process layer or chromating layer Surface carry out surface treatment documented by following patents: International Publication number WO2008/053878, Japanese Unexamined Patent Publication 2008- No. 111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. 4828427, state Border discloses number WO2006/134868, Japanese Patent No. 5046927, International Publication number WO2007/105635, Japan specially Benefit No. 5180815, Japanese Unexamined Patent Publication 2013-19056.
Furthermore it can also be on a surface of very thin layers of copper or the setting of two surfaces selected from by roughening treatment layer, refractory layer, antirust The layer of one or more of group composed by layer, chromating layer and silane coupling process layer, may also set up surface-treated layer. Surface-treated layer can also be for selected from by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer institute The layer of one or more of the group of composition.
Also, Copper foil with carrier can also have one layer or more selected from by refractory layer, antirust coat, chromium on above-mentioned roughening treatment layer Layer in group composed by hydrochlorate process layer and silane coupling process layer.
Also, can also have refractory layer, antirust coat on above-mentioned roughening treatment layer, it can also on above-mentioned refractory layer, antirust coat Have chromating layer, can also have silane coupling process layer on above-mentioned chromating layer.
Also, above-mentioned Copper foil with carrier can also be in above-mentioned very thin layers of copper or on above-mentioned roughening treatment layer or above-mentioned heat-resisting Has resin layer in layer, antirust coat or chromating layer or silane coupling process layer.Above-mentioned resin layer can also be insulating resin Layer.
Also, Copper foil with carrier can have roughening treatment layer on carrier, can also have on carrier one layer or more selected from by Layer in group composed by roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer.It is above-mentioned thick Changing process layer, refractory layer, antirust coat, chromating layer and silane coupling process layer can be arranged using well known method, It can be arranged by the method recorded in present specification, claim, schema.Carrier had into above-mentioned roughening treatment certainly The surface side lamination of layer etc. is arranged one layer or more at above-mentioned roughening in the situation of the supports such as resin substrate on carrier Managing the case where layer, refractory layer, antirust coat, chromating layer, silane are coupled the layer in process layer has carrier and support not Easily peelable advantage.
Above-mentioned resin layer can be solid, can also be for then with the insulating resin layer of semi-hardened state (B-stage state).Half Hardening state (B-stage state) includes following states: also feels without adhesion even if touching its surface with finger, it can be by the insulating resin Layer overlaps and takes care of, if further progress heats, can cause sclerous reaction.
Also, above-mentioned resin layer can contain thermosetting resin, it can also be thermoplastic resin.Also, above-mentioned resin layer can also contain There is thermoplastic resin.Above-mentioned resin layer can also contain well known resin, hardening of resin agent, compound, hardening accelerator, dielectric Body, catalysts, crosslinking agent, polymer, prepreg, framework material etc..Also, following document for example can be used in above-mentioned resin layer In documented substance it is (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, catalysts, crosslinking agent, poly- Close object, prepreg, framework material etc.) and/or resin layer forming method, form device and formed, the document is International Publication Number WO2008/004399, International Publication number WO2008/053878, International Publication number WO2009/084533, Japan Japanese Laid-Open Patent Publication 11-5828, Japanese Unexamined Patent Publication 11-140281, Japanese Patent No. 3184485, International Publication number WO97/ 02728, Japanese Patent No. 3676375, Japanese Unexamined Patent Publication 2000-43188, Japanese Patent No. 3612594, Japanese Unexamined Patent Publication No. 2002-179772, Japanese Unexamined Patent Publication 2002-359444, Japanese Unexamined Patent Publication 2003-304068, Japanese Patent No. No. 3992225, Japanese Unexamined Patent Publication 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication No. 2004-82687, day This patent the 4025177th, Japanese Unexamined Patent Publication 2004-349654, Japanese Patent No. 4286060, Japanese Unexamined Patent Publication 2005- No. 262506, Japanese Patent No. 4570070, Japanese Unexamined Patent Publication 2005-53218, Japanese Patent No. 3949676, Japan specially Benefit No. 4178415, International Publication number WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007- No. 326923, Japanese Unexamined Patent Publication 2008-111169, Japanese Patent No. 5024930, International Publication number WO2006/ 028207, Japanese Patent No. 4828427, Japanese Unexamined Patent Publication 2009-67029, International Publication number WO2006/134868, day This patent the 5046927th, Japanese Unexamined Patent Publication 2009-173017, International Publication number WO2007/105635, Japanese Patent No. No. 5180815, International Publication number WO2008/114858, International Publication number WO2009/008471, Japanese Unexamined Patent Publication 2011- No. 14727, International Publication number WO2009/001850, International Publication number WO2009/145179, International Publication number WO2011/068157, Japanese Unexamined Patent Publication No. 2013-19056 number.
Also, the type of above-mentioned resin layer is not particularly limited, as preferably, such as can enumerate containing being selected from following ingredient One or more of group resin: epoxy resin, polyimide resin, multi-functional cyanate esters, maleoyl- Group with imine moiety, poly- maleimide compounds, maleimide system resin, aromatic series maleimide tree Rouge, polyvinyl acetal resin, amine ester (urethane) resin, polyether sulfone (also referred to as polyethersulphone, Polyethersulfone), polyether sulfone (also referred to as polyethersulphone, polyethersulfone) resin, aromatic series Polyamide, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamidoimide tree Rouge, rubber modified epoxy resin, phenoxy resin, carboxyl modify acrylonitrile-butadiene resin, polyphenylene oxide, double maleoyl-s Imines cyanate resin, thermosetting polyphenylene oxide resin, cyanate ester system resin, the acid anhydrides of carboxylic acid, polybasic carboxylic acid acid anhydrides, have Bis- (4- cyanatephenyl) propane of linear polymer, polyphenylene oxide resin, the 2,2- of crosslinkable functional group, phosphorous phenolate It closes object, manganese naphthenate, bis- (the 4- glycidyl phenyl) propane of 2,2-, polyphenylene oxide-cyanate ester based resin, siloxanes and modifies and gather Amide imide resin, hydrocyanic ester resin, phosphine nitrile system resin, rubber modified polyamide-imide resin, isoprene, hydrogenation type are poly- Butadiene, polyvinyl butyral, phenoxy group, macromolecule epoxy resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerization polyamides Imide resin and hydrocyanic ester resin.
Also, above-mentioned epoxy resin intramolecular has 2 or more epoxy group persons, as long as and to can be used for electrical property, electronics Material applications then can be used especially without problems.Also, above-mentioned epoxy resin preferably uses intramolecular to have 2 or more epoxies The compound of propyl carries out epoxy resin made of epoxidation.Also, can by a kind in the group as composed by following ingredient or Two or more mixes and uses: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D-ring Oxygen resin, phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, bromination (brominated) epoxy resin, phenol system phenolic resin varnish type epoxy resin, naphthalene type epoxy resin, brominated bisphenol a type epoxy resin, O-cresol phenolic epoxy varnish, rubber modified bisphenol A type epoxy resin, epoxy propylamine type epoxy resin, isocyanuric acid Three polyglycidyls, N, the epoxies such as epoxy propylamines compound, the tetrahydrophthalic acid diglycidyl ether such as N- diepoxy propyl aniline Propyl ester compound, phosphorous epoxy resin, biphenyl type epoxy resin, biphenyl phenolic resin varnish type epoxy resin, trihydroxy phenyl first Alkane type epoxy resin, tetraphenyl ethane type epoxy resin, or the hydrogenation body or halogenation body of above-mentioned epoxy resin can be used.
Contain the epoxy resin of phosphorus as above-mentioned phosphorous epoxy resin well known to can be used.Also, above-mentioned phosphorous epoxy Resin be preferably such as intramolecular have 2 or more epoxy groups with from the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy The epoxy resin that the form of the derivative of 10- oxide obtains.
(resin layer contains the case where dielectric substance (dielectric substance filler))
Above-mentioned resin layer can also contain dielectric substance (dielectric substance filler).
When containing the situation of dielectric substance (dielectric substance filler) in any of the above-described kind of resin layer or resin combination, can use In the purposes of formation capacitor layer, and increase the capacitor of capacitor circuit.The dielectric substance (dielectric substance filler) is using BaTiO3、 SrTiO3, Pb (Zr-Ti) O3(common name PZT), PbLaTiO3PbLaZrO (common name PLZT), SrBi2Ta2O9(common name SBT) etc. The dielectric substance powder of composite oxides with perovskite (Perovskite) structure.
Dielectric substance (dielectric substance filler) can also be powdery.When dielectric substance (dielectric substance filler) is the situation of powdery, Jie The powder characteristics of electric body (dielectric substance filler) is preferably the model that partial size is 0.01 μm~3.0 μm, preferably 0.02 μm~2.0 μm It encloses.Furthermore photo is shot to dielectric substance using scanning electron microscope (SEM), in the particle of the dielectric substance on the photo On when drawing the situation of straight line, the particle length for the dielectric substance that the straight length of the particle of crosscutting dielectric substance is longest part is set For the particle diameter of the dielectric substance.Also, the average value of the particle diameter of the dielectric substance measured in the visual field is set as dielectric substance Partial size.
Resin contained in above-mentioned resin layer and/or resin combination and/or compound is set to be dissolved in such as Methylethyl Ketone (MEK), cyclopentanone, dimethylformamide, dimethyl acetamide, N- methylpyrrole pyridine ketone, toluene, methanol, ethyl alcohol, the third two Alcohol monomethyl ether, dimethylformamide, dimethyl acetamide, cyclohexanone, ethyl Cellosolve, N- methyl -2- Pyrrolizidine ketone, N, Resin liquid (resin varnish) is made in N- dimethyl acetamide, n,N-Dimethylformamide equal solvent, for example, by roll-type Rubbing method etc. is coated on the very thin layers of copper side surface of above-mentioned Copper foil with carrier, is then optionally thermally dried, removal Solvent and become B-stage state.As long as dry for example using hot-air drying stove, if drying temperature be 100~250 DEG C, Preferably 130~200 DEG C.Usable solvent dissolves the constituent of above-mentioned resin layer, and resin solid content ingredient is made 3wt%~70wt%, preferably 3wt%~60wt%, preferably 10wt%~40wt%, more preferably 25wt%~40wt% Resin liquid.Furthermore for the viewpoint of atmosphere, at this stage most preferably using methyl ethyl ketone and cyclopentanone mixed solvent into Row dissolution.Furthermore solvent is preferably to use boiling point for the solvent of 50 DEG C~200 DEG C of range.
Also, above-mentioned resin layer is preferably resin flowing when being measured according to the MIL-P-13949G in MIL standard The semi-hardened resin film for the range that amount is 5%~35%.
In the specification of the present application, so-called resin flow refers to according to the MIL-P-13949G in MIL standard, certainly So that the surface treatment copper foil of 55 μm of resin thickness of attached resin is taken 4 10cm square samples, 4 samples is made to overlap Under state (laminate), in 171 DEG C of press temperature, pressing pressure 14kgf/cm2, pasted under conditions of 10 minutes pressing times It closes, it is resulting as a result, the value calculated based on number 1 according to the resin outflow weight of measurement at this time.
[mathematical expression 1]
The surface treatment copper foil (surface treatment copper foil of attached resin) for having above-mentioned resin layer is with the use of following aspect: will Overall thermal is crimped after overlapping with substrate and makes the resin layer thermmohardening by the resin layer, is then appendix body in surface treatment copper foil When the situation of the very thin layers of copper of copper foil, remove carrier and expose very thin layers of copper (expose certainly be the very thin layers of copper middle layer Side surface), specific Wiring pattern is formed from the surface with the roughening treatment side of surface treatment copper foil phase side on the contrary.
If prepreg material when manufacture multilayer printed wiring board can be reduced using the surface treatment copper foil of the attached resin The use the piece number of material.Even if moreover, the thickness of resin layer is set as to can ensure that the thickness of layer insulation, or completely without using preimpregnation Body material can also manufacture copper-cover laminated plate.Also, at this point, insulating resin priming paint can also be coated on to the surface of substrate and further Improve the flatness on surface.
Furthermore when not using the situation of prepreg material, the material cost of prepreg material can be saved, in addition, lamination step Suddenly also become simple, therefore economically advantageously, and have the following advantages: only manufacturing the thickness degree of prepreg material The thickness of multilayer printed wiring board is thinning, and can manufacture 1 layer with a thickness of 100 μm of very thin multi-sheet printed wiring bases below Plate.
The thickness of the resin layer is preferably 0.1~120 μm.
If the thickness of resin layer is thinner than 0.1 μm, have following situation: adhesion is reduced, and deposits prepreg material general not being situated between The surface treatment copper foil lamination of the attached resin is when on the substrate for have inner layer material, it is difficult to ensure between inner layer material and circuit Layer insulation.On the other hand, if the thickness of resin layer is thicker than 120 μm, there is following situation: being difficult in 1 application step The resin layer of target thickness is formed, and needs extra fee of material and number of steps, so economically become unfavorable.
Furthermore in the situation that will there is the surface treatment copper foil of resin layer to be used to manufacture very thin multi-layer printed circuit board When, it, can when the thickness of above-mentioned resin layer is set as 0.1 μm~5 μm, more preferably 0.5 μm~5 μm, more preferably 1 μm~5 μm The thickness of multi-layer printed circuit board is reduced, so it is preferred that.
In turn, by the electronic component mounting class on printing distributing board, and printed circuit board is completed.In the present invention, " print Brush distributing board " is also including the printing distributing board and printed circuit board and printed base plate so equipped with electronic component class.
Also, the printing distributing board can be used and make e-machine, the printing electricity equipped with the electronic component class can be used Road plate and make e-machine, it is possible to use the printed base plate equipped with the electronic component class and make e-machine.Hereinafter, table Show the example of the manufacturing step of several printing distributing boards using Copper foil with carrier of the invention.
One embodiment of the manufacturing method of printing distributing board of the invention includes following step: preparing appendix of the invention Body copper foil and insulating substrate；By above-mentioned Copper foil with carrier and insulating substrate lamination；And so that very thin layers of copper side and insulating substrate pair To mode by after above-mentioned Copper foil with carrier and insulating substrate lamination, through the step of carrier of above-mentioned Copper foil with carrier is removed Copper-cover laminated plate is formed, thereafter, passes through any side in semi-additive process, improvement semi-additive process, part addition process and subtractive process Method forms circuit.Insulating substrate can also be set as internal layer circuit entrance.
In the present invention, so-called semi-additive process, refer to carried out on insulating substrate or copper foil seed layer it is relatively thin electroless Plating after forming pattern, using plating and etches the method for forming conductive pattern.
It therefore, a use of embodiment of the manufacturing method of the printing distributing board of the invention of semi-additive process include following steps It is rapid:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
The very thin layers of copper that will be removed above-mentioned carrier by using the methods of the etching of the etchant solutions such as acid or plasma-based and expose It completely removes；
Through-hole and/or blind hole are set on the above-mentioned resin exposed and removing above-mentioned very thin layers of copper using etching；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
In the region containing above-mentioned resin and above-mentioned through-hole and/or blind hole, electroless plating coating is set；
Photoresist is set on above-mentioned electroless plating coating；
Above-mentioned photoresist is exposed, thereafter, removal is formed with the photoresist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned photoresist；
Remove above-mentioned photoresist；And
By the removals such as fast-etching be located in addition to it is above-mentioned be formed with the region of circuit other than region electroless plating Layer.
Another embodiment using the manufacturing method of the printing distributing board of the invention of semi-additive process includes following step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on above-mentioned insulating resin substrate removing above-mentioned carrier and exposing；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
The very thin layers of copper that will be removed above-mentioned carrier by using the methods of the etching of the etchant solutions such as acid or plasma-based and expose It completely removes；
Containing the above-mentioned resin and above-mentioned through-hole and/or blind hole by exposing using the above-mentioned very thin layers of copper of the removal such as etching Region be arranged electroless plating coating；
Photoresist is set on above-mentioned electroless plating coating；
Above-mentioned photoresist is exposed, thereafter, removal is formed with the photoresist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned photoresist；
Remove above-mentioned photoresist；And
By the removals such as fast-etching be located in addition to it is above-mentioned be formed with the region of circuit other than region electroless plating Layer.
Another embodiment using the manufacturing method of the printing distributing board of the invention of semi-additive process includes following step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on above-mentioned insulating resin substrate removing above-mentioned carrier and exposing；
The very thin layers of copper that will be removed above-mentioned carrier by using the methods of the etching of the etchant solutions such as acid or plasma-based and expose It completely removes；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
Containing the above-mentioned resin and above-mentioned through-hole that expose and using the above-mentioned very thin layers of copper of removal such as etching and/or blind Electroless plating coating is arranged in the region in hole；
Photoresist is set on above-mentioned electroless plating coating；
Above-mentioned photoresist is exposed, thereafter, removal is formed with the photoresist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned photoresist；
Remove above-mentioned photoresist；And
By the removals such as fast-etching be located in addition to it is above-mentioned be formed with the region of circuit other than region electroless plating Layer.
Another embodiment using the manufacturing method of the printing distributing board of the invention of semi-additive process includes following step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
The very thin layers of copper that will be removed above-mentioned carrier by using the methods of the etching of the etchant solutions such as acid or plasma-based and expose It completely removes；
On the surface of the above-mentioned resin exposed and removing above-mentioned very thin layers of copper using etching, electroless plating coating is set；
Photoresist is set on above-mentioned electroless plating coating；
Above-mentioned photoresist is exposed, thereafter, removal is formed with the photoresist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned photoresist；
Remove above-mentioned photoresist；And
By the removals such as fast-etching be located in addition to it is above-mentioned be formed with the region of circuit other than region electroless plating Layer and very thin layers of copper.
In the present invention, so-called improvement semi-additive process, refers to lamination metal foil on the insulating layer, is protected by photoresist non- Circuit forming portion, by be electrolysed plating thicken circuit forming portion copper it is thick after, remove resist, (quick) etching utilized to remove The metal foil other than circuit forming portion is stated, the method for circuit is thus formed on the insulating layer.
Therefore, under including using an embodiment of the manufacturing method for the printing distributing board of the invention for improving semi-additive process State step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on insulating substrate removing above-mentioned carrier and exposing；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
Electroless plating coating is set containing the region of through-hole and/or blind hole above-mentioned；
On the very thin layers of copper surface removing above-mentioned carrier and exposing, photoresist is set；
After above-mentioned photoresist is set, circuit is formed by electrolysis plating；
Remove above-mentioned photoresist；And
The very thin layers of copper exposed using fast-etching removal by removing above-mentioned photoresist.
Another embodiment using the manufacturing method for the printing distributing board of the invention for improving semi-additive process includes following Step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
Photoresist is set in the very thin layers of copper that the above-mentioned carrier of removing exposes；
Above-mentioned photoresist is exposed, thereafter, removal is formed with the photoresist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned photoresist；
Remove above-mentioned photoresist；And
By the removals such as fast-etching be located in addition to it is above-mentioned be formed with the region of circuit other than region very thin layers of copper.
In the present invention, so-called part addition process, refer to be arranged substrate made of conductor layer, optionally pass through through-hole or Catalysis core is assigned on substrate made of via hole hole, is etched to form conductor circuit, and solder resist or photoresist are optionally set After agent, on above-mentioned conductor circuit by electroless plating handle (optionally further progress be electrolysed plating processing) to through-hole or Via hole etc. is thickened, and the method for printing distributing board is thus manufactured.
It therefore, a use of embodiment of the manufacturing method of the printing distributing board of the invention of part addition process include following Step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on insulating substrate removing above-mentioned carrier and exposing；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
Catalysis core is assigned containing the region of through-hole and/or blind hole above-mentioned；
In the very thin layers of copper surface setting etching resist removing above-mentioned carrier and exposing；
Above-mentioned etching resist is exposed and forms circuit pattern；
Above-mentioned very thin layers of copper and above-mentioned catalysis core are removed using the methods of etching or plasma-based for using the etchant solutions such as acid, and Form circuit；
Remove above-mentioned etching resist；
Above-mentioned very thin layers of copper and above-mentioned catalysis core are being removed using the methods of the etching or plasma-based that use the etchant solutions such as acid And the above-mentioned insulating substrate surface exposed, solder resist or photoresist are set；And
In the region of not set above-mentioned solder resist or photoresist, electroless plating coating is set.
In the present invention, so-called subtractive process refers to the unwanted portion of the copper foil on copper-cover laminated plate through etching etc. The method for removing, and forming conductive pattern to component selections.
It therefore, a use of embodiment of the manufacturing method of the printing distributing board of the invention of subtractive process include following steps It is rapid:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on insulating substrate removing above-mentioned carrier and exposing；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
Electroless plating coating is set containing the region of through-hole and/or blind hole above-mentioned；
In the surface of above-mentioned electroless plating coating setting electrolysis plating layer；
On the surface of above-mentioned electrolysis plating layer and/or above-mentioned very thin layers of copper, etching resist is set；
Above-mentioned etching resist is exposed and forms circuit pattern；
Above-mentioned very thin layers of copper and above-mentioned electroless plating are removed using the methods of etching or plasma-based for using the etchant solutions such as acid Coating and above-mentioned electrolysis plating layer, and form circuit；And
Remove above-mentioned etching resist.
Another embodiment using the manufacturing method of the printing distributing board of the invention of subtractive process includes following step:
Prepare Copper foil with carrier and insulating substrate of the invention；
By above-mentioned Copper foil with carrier and insulating substrate lamination；
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the carrier of above-mentioned Copper foil with carrier is removed；
In the very thin layers of copper and setting through-hole and/or blind hole on insulating substrate removing above-mentioned carrier and exposing；
De-smear processing is carried out to the region containing above-mentioned through-hole and/or blind hole；
Electroless plating coating is set containing the region of through-hole and/or blind hole above-mentioned；
Mask is formed on the surface of above-mentioned electroless plating coating；
In the surface setting electrolysis plating layer of the above-mentioned electroless plating coating of not formed mask；
On the surface of above-mentioned electrolysis plating layer and/or above-mentioned very thin layers of copper, etching resist is set；
Above-mentioned etching resist is exposed and forms circuit pattern；
Above-mentioned very thin layers of copper and above-mentioned electroless plating are removed using the methods of etching or plasma-based for using the etchant solutions such as acid Coating, and form circuit；And
Remove above-mentioned etching resist.
Can also be without setting through-hole and/or blind hole the step of and subsequent de-smear step.
The manufacturing method of printing distributing board of the invention also may include following step: in the upper of Copper foil with carrier of the invention The step of stating surface-treated layer side surface or above-mentioned carrier side circuit forming surface, by foregoing circuit embedment in a manner of above-mentioned attached The above-mentioned surface-treated layer side surface of carrier copper foil or above-mentioned carrier side surface form the step of resin layer, on above-mentioned resin layer The step of the step of forming circuit forms after circuit on above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed, And after removing above-mentioned carrier or above-mentioned very thin layers of copper, by removing above-mentioned very thin layers of copper or above-mentioned carrier, and make to be formed in State the step of circuit for being embedded in above-mentioned resin layer of surface-treated layer side surface or above-mentioned carrier side surface exposes.Also, printing The manufacturing method of distributing board also may include following step: Copper foil with carrier of the invention above-mentioned surface-treated layer side surface or The step of above-mentioned carrier side circuit forming surface, by foregoing circuit embedment in a manner of at the above-mentioned surface of above-mentioned Copper foil with carrier The step of managing layer side surface or above-mentioned carrier side surface formation resin layer, the step for removing above-mentioned carrier or above-mentioned very thin layers of copper Suddenly and after the above-mentioned carrier of removing or above-mentioned very thin layers of copper, by removing above-mentioned very thin layers of copper or above-mentioned carrier, and make to be formed in The step of circuit for being embedded in above-mentioned resin layer of above-mentioned surface-treated layer side surface or above-mentioned carrier side surface exposes.
Herein, the manufacturing method using the printing distributing board for having Copper foil with carrier of the invention is explained in detail using schema Specific embodiment.Furthermore roughening treatment layer herein, is formed with as the appendix of the very thin layers of copper of surface-treated layer to have It is illustrated for body copper foil, it is not the Copper foil with carrier for being roughening treatment layer using the surface-treated layer that but it is not limited to this, The manufacturing method of following printing distributing boards can also be carried out similarly.
Firstly, as shown in Figure 1A, preparing the Copper foil with carrier (for the very thin layers of copper that there is surface to be formed with roughening treatment layer 1 layer).
Secondly, as shown in Figure 1B, be coated with resist on the roughening treatment layer of very thin layers of copper, be exposed, develop and incite somebody to action Resist is etched to specific shape.
Secondly, as shown in Figure 1 C, by removing resist after forming circuit coating, and forming the circuit of specific shape Coating.
Secondly, as shown in Figure 2 D, in very thin layers of copper (in a manner of burying circuit coating) in a manner of coating circuit coating Upper setting is embedded to resin and laminated resin layer, then flanks another Copper foil with carrier (the 2nd layer) from very thin layers of copper.
Secondly, as shown in Figure 2 E, removing carrier from the 2nd layer of Copper foil with carrier.
Secondly, as shown in Figure 2 F, carrying out laser aperture in the specific position of resin layer, circuit coating being made to expose and be formed blind Hole.
Secondly, as shown in Figure 3 G, copper is embedded in blind hole, through-hole filler is formed.
Secondly, as shown in figure 3h, on through-hole filler, forming circuit plating in a manner of above-mentioned Fig. 1-B and Fig. 1-C Layer.
Secondly, as shown in fig. 31, removing carrier from the 1st layer of Copper foil with carrier.
Secondly, as shown in fig. 4j, the very thin layers of copper on two surfaces being removed by fast-etching, makes the circuit coating in resin layer Surface expose.
Secondly, as shown in Figure 4 K, forming convex block on the circuit coating in resin layer, forming copper post on the solder.Such as This production uses the printing distributing board for having Copper foil with carrier of the invention.
Copper foil with carrier of the invention can be used in above-mentioned another Copper foil with carrier (the 2nd layer), and previous appendix body can be used Copper foil, and then common copper foil can also be used.Also, 1 layer or multilayer electricity can be further formed on the 2nd layer of circuit shown in Fig. 3 H Road can form the electricity such as this by any method in semi-additive process, subtractive process, part addition process or improvement semi-additive process Road.
Also, Copper foil with carrier used in above-mentioned 1st layer can also have substrate in the carrier side surface of the Copper foil with carrier. By having the substrate, Copper foil with carrier used in the 1st layer is supported, becomes to be not likely to produce gauffer, therefore have productivity The advantages of raising.Furthermore as long as the effect of Copper foil with carrier used in above-mentioned 1st layer of support of aforesaid substrate performance, can make With whole substrates.For example, carrier, prepreg, resin layer or the well known carrier, preimpregnation recorded in present specification can be used Body, resin layer, metal plate, metal foil, the plate of inorganic compound, the foil of inorganic compound, the plate of organic compound, organic compound The foil of object is as aforesaid substrate.
At the time point that carrier side surface forms substrate, there is no particular restriction, but must be formed before removing carrier.Especially It is preferably to be formed the step of forming resin layer in the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier before, more preferably To be formed the step of forming circuit in the above-mentioned very thin layers of copper side surface of Copper foil with carrier before.
Furthermore being embedded to resin (resin) can be used well known resin, prepreg.Such as BT (double maleoyl-s can be used Imines triazine) resin or it is impregnated with glass cloth, that is, prepreg of BT resin, Ajinomoto Fine-Techno limited liability company The ABF film or ABF of manufacture.Also, above-mentioned embedment resin can contain thermosetting resin, it can also be thermoplastic resin.Also, above-mentioned bury Thermoplastic resin can also be contained by entering resin.The type of above-mentioned embedment resin is not particularly limited, and as preferred person, such as can be arranged It lifts: including epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compounds, polyethylene Tree including alcohol acetate resin, amine ester resin, block copolymerization polyimide resin, block copolymerization polyimide resin etc. Rouge 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 nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, polyester film, polyamides Imines film, liquid crystalline polymer film, fluororesin film etc..
Also, the manufacturing method of printing distributing board of the invention can also be the manufacturer of the printing distributing board comprising following step Method (called non-sleeve method): by the above-mentioned very thin layers of copper side surface of Copper foil with carrier of the invention or above-mentioned carrier side surface and resin substrate The step of carrying out lamination；It is being opposite with above-mentioned and resin substrate layer surface-treated layer side surface or above-mentioned carrier side surface The step of this two layers of 1 resin layer and circuit is at least arranged in the surface of the Copper foil with carrier of side；And formed above-mentioned resin layer and After this two layers of circuit, above-mentioned carrier is removed from above-mentioned Copper foil with carrier or the step of above-mentioned very thin layers of copper.About above-mentioned called non-sleeve method, As specific example, firstly, by the surface-treated layer side surface of Copper foil with carrier of the invention or carrier side surface and resin Substrate carries out lamination.Then, with resin substrate layer surface-treated layer side surface or above-mentioned carrier side surface be it is opposite The surface of the Copper foil with carrier of side forms resin layer.It can also be in the tree for being formed in carrier side surface or surface-treated layer side surface Rouge layer is from carrier side or surface-treated layer side and then another Copper foil with carrier of lamination.In the case, at being constructed as follows: with It is suitable with carrier/middle layer/very thin layers of copper/surface-treated layer in two surface sides of above-mentioned resin substrate centered on resin substrate Sequence or with surface-treated layer/very thin layers of copper/middle layer/carrier sequential lamination Copper foil with carrier.It can also be on the surface at both ends Another resin layer is arranged in the surface that process layer or carrier are exposed, and layers of copper or metal layer are arranged in turn, then to above-mentioned layers of copper Or metal layer is processed, and circuit is consequently formed.And then another resin layer can also be arranged in a manner of filling foregoing circuit On foregoing circuit.Also, can also be by the formation of such circuit and resin layer progress 1 time or more (Layer increasing method).Also, about with The laminate (hereinafter also referred to laminate B) that aforesaid way is formed, can by the very thin layers of copper of each Copper foil with carrier or carrier from Carrier or very thin layers of copper are removed and make coreless substrate.In addition, 2 appendix also can be used when making above-mentioned coreless substrate Body copper foil makes following with surface-treated layer/very thin layers of copper/middle layer/carrier/carrier/middle layer/very thin layers of copper/surface The laminate of the composition of process layer has carrier/middle layer/very thin layers of copper surface-treated layer/surface-treated layer/very thin copper The laminate of layer/middle layer/carrier composition has carrier/middle layer/very thin layers of copper/surface-treated layer/carrier/centre The laminate of layer/very thin layers of copper/surface-treated layer composition, and above-mentioned laminate is used for center.It can be in these laminates This two layers of resin layer and circuit is arranged 1 time or more in the surface of the very thin layers of copper of the two sides of (hereinafter also referred to laminate A) or carrier, After this two layers of 1 time or more resin layer of setting and circuit, by the very thin layers of copper of each Copper foil with carrier or carrier from carrier or very thin Layers of copper is removed and makes coreless substrate.Above-mentioned laminate between the surface of surface-treated layer, surface-treated layer and very thin layers of copper, Between the surface of carrier, carrier and carrier, between surface-treated layer and surface-treated layer, can also be between very thin layers of copper and carrier With other layers.In addition, in this specification, " surface of surface-treated layer ", " surface-treated layer side surface ", " table of carrier Face ", " carrier side surface ", " carrier surface ", " surface of laminate ", " laminate surface ", when surface-treated layer, carrier, product Layer body is set in the case where being surface-treated layer surface, carrier surface, laminate surface with other layers comprising above-mentioned other The concept on the surface (most surface) of layer.Also, laminate preferably have surface-treated layer/very thin layers of copper/middle layer/carrier/carrier/ Middle layer/very thin layers of copper/surface-treated layer composition.This is because: when stating laminate production coreless substrate in use, because Configure very thin layers of copper in coreless substrate side, thus improvement semi-additive process easy to use and circuit is formed on coreless substrate.Also, being By: because the thickness of very thin layers of copper is thin, easily remove above-mentioned very thin layers of copper, remove after very thin layers of copper easy to use half plus Circuit is formed on coreless substrate at method.
In addition, in the present specification, " laminate " for not being recorded into " laminate A " or " laminate B " especially indicates extremely It less include the laminate of laminate A and laminate B.
Furthermore in the manufacturing method of above-mentioned coreless substrate, by covering Copper foil with carrier or laminate (product using resin Layer body A) end face part or all, using Layer increasing method manufacture printing distributing board when, can prevent chemical solvent from penetrating into To between middle layer or a piece of Copper foil with carrier and another Copper foil with carrier of composition laminate, can prevent by chemical solvent Infiltration caused by the separation of very thin layers of copper and carrier or the corrosion of Copper foil with carrier, yield can be promoted.As this place Use " covering Copper foil with carrier end face some or all of resin " or " covering laminate end face a part or Whole resin ", can be used the resin that can be used in resin layer.Also, in the manufacturing method of above-mentioned coreless substrate, to attached When carrier copper foil or laminate are overlooked, the lamination part (lamination of carrier and very thin layers of copper of Copper foil with carrier or laminate Partially or the lamination part of a piece of Copper foil with carrier and another Copper foil with carrier) at least part of periphery can be by setting Rouge or prepreg covering.It is also possible in addition, being formed by laminate (laminate A) using the manufacturing method of above-mentioned coreless substrate A pair of of Copper foil with carrier is set mutually to contact and constitute in a detachable fashion.Also, when overlooking above-mentioned Copper foil with carrier, It can also be by resin or lamination part (the lamination portion of carrier and very thin layers of copper of prepreg covering Copper foil with carrier or laminate Point or a piece of Copper foil with carrier and another Copper foil with carrier lamination part) periphery it is whole.By being set as such composition, When overlooking Copper foil with carrier or laminate, the lamination part of Copper foil with carrier or laminate is covered by resin or prepreg, can With prevent other components from the side of this part to, namely relative to lamination direction be that lateral direction is collided, as a result, can subtract Carrier and very thin layers of copper or the mutual removing of Copper foil with carrier in few operation.Also, by not expose Copper foil with carrier or lamination The mode of the periphery of the lamination part of body is covered using resin or prepreg, can prevent chemical solvent as described above from handling In step interface from chemical solvent to above-mentioned lamination part infiltration, the corrosion or erosion of Copper foil with carrier can be prevented.Furthermore When separating a piece of Copper foil with carrier from a pair of of Copper foil with carrier of laminate, or the carrier and copper foil of separation Copper foil with carrier When (very thin layers of copper), it is necessary to pass through the lamination of Copper foil with carrier or laminate that the removals such as cutting are covered using resin or prepreg Partially (the lamination part or a piece of Copper foil with carrier of carrier and very thin layers of copper and the lamination part of another Copper foil with carrier).
It can also be of the invention at another from carrier side or surface-treated layer side lamination by Copper foil with carrier of the invention Carrier side or the surface-treated layer side of Copper foil with carrier and constitute laminate.Also, can also be following laminates: above-mentioned a piece of appendix The above-mentioned carrier side surface or above-mentioned surface-treated layer side surface of body copper foil and the above-mentioned carrier of above-mentioned another Copper foil with carrier Side surface or above-mentioned surface-treated layer side surface, the optionally winner via solid direct lamination.Also, can also be by above-mentioned one The carrier or surface-treated layer of piece Copper foil with carrier and the engagement of the carrier or surface-treated layer of above-mentioned another Copper foil with carrier. Also, part or all of the end face of the laminate can also be covered by resin.
The mutual lamination of carrier is other than merely overlapping, such as can use following methods progress.
(a) metallurgical, bond method: welding (arc welding, TIG (tungsten inert gas, tungsten-inert gas) weldering Connect, MIG (metal inert gas, metal-noble gas) welding, resistance welding, seam welding, spot welding), crimping (Supersonic Wave soldering connects, friction stir weld), soft soldering；
(b) mechanical interface method: caulk, using rivet engagement (using the engagement of self-pierce riveting, utilizing the engagement of rivet), Binder；
(c) physical engagement method: solid, (two-sided) adhesive tape
By by part or all and another carrier of a carrier part or all using above-mentioned joint method into Row engagement, can manufacture the product for contacting carrier in a detachable fashion each other a carrier and another carrier lamination and constituting Layer body.If a carrier and another carrier weaker connect, by a carrier and another carrier lamination, even if not going Except the interconnecting piece of a carrier and another carrier, a carrier and another carrier can also be separated.In addition, in a carrier and another load In the case that body connects strongly, cutting or chemical grinding (etching are utilized by the position for connecting a carrier with another carrier Deng), the removal such as mechanical lapping, a carrier and another carrier can be separated.
Also, printing distributing board can be made and performing the following steps: the laminate constituted in the above described manner at least The step of this two layers of 1 resin layer and circuit are set；And after at least forming this two layers of 1 above-mentioned resin layer and circuit, from upper The step of stating the above-mentioned very thin layers of copper of Copper foil with carrier removing or carrier of laminate.Furthermore it can also be at one of the laminate Surface or this two layers of two surfaces setting resin layers and circuit.
[embodiment]
Hereinafter, being illustrated based on experimental example.Furthermore this experimental example only as an example of, be not limited to the example.
1. the manufacture of Copper foil with carrier
Using sequence below, Copper foil with carrier is made.
Firstly, the long electrolytic copper foil or rolled copper foil that prepare thickness documented by table 1 are as carrier.
Electrolytic copper foil is manufactured using following conditions.
(electrobath composition)
Cu:80~120g/L
H2SO4: 80~120g/L
Cl:20~80mg/L
Varnish: 0.1~6.0mg/L
(electrolytic condition)
Liquid temperature: 55~65 DEG C
Current density: 100A/dm2
Electrolyte flow rate: 1.5m/ seconds
Rolled copper foil is using refined copper (refined copper of JIS H3100 C1100 defined) in example 9,12, is to make in example 10,11 With oxygen-free copper (oxygen-free copper of JIS H3100 C1020 defined)." the rolled copper foil on the type column of the carrier of table 1 (Ag180ppm) " refer to the Ag that 180 mass ppm are added in refined copper.
The middle layer > of < embodiment
Utilize the following conditions in the continuous plating wiring of roll-to-roll type the glassy surface (shiny surface) of above-mentioned copper foil On, middle layer is formed by plating.
Ni layers
Nickel sulfate: 250~300g/L
Nickel chloride: 35~45g/L
Nickel acetate: 10~20g/L
Trisodium citrate: 15~30g/L
Gloss agent: saccharin, butynediols etc.
Lauryl sodium sulfate: 30~100ppm
PH:4~6
Bath temperature: 50~70 DEG C
Current density: 3~15A/dm2
Adhesion amount: 4000 μ g/dm2
After washing and pickling, then on the continuous plating wiring of roll-to-roll type, pass through electrolysis chromic acid using the following conditions Salt treatment and make 10 μ g/dm of adhesion amount2Cr layer be attached on Ni layer.
Electrolytic chromate processing
Liquid composition: 1~10g/L of potassium bichromate, 0~5g/L of zinc
PH:3~4
Liquid temperature: 50~60 DEG C
Current density: 0.1~2.6A/dm2
Coulomb amount: 0.5~30As/dm2
The very thin layers of copper > of < embodiment
Then, on the continuous plating wiring of roll-to-roll type, thickness is formed by plating on the intermediate layer using the following conditions The very thin layers of copper of 3 μm of degree, so that Copper foil with carrier be made.
Very thin layers of copper
Copper concentration: 30~120g/L
H2SO4Concentration: 20~120g/L
Electrolyte temperature: 20~80 DEG C
Current density: 10~100A/dm2
The surface-treated layer > of < embodiment
The surface of above-mentioned very thin layers of copper is surface-treated using surface treatment condition below.The surface will be passed through The layer of the surface-treated layer of processing and formation constitutes shown in table 1.
In a part of embodiment, the surface of above-mentioned very thin layers of copper is carried out with following conditions selected from Cu-W Alloy Plating One of deposited, Cu-P alloy plated, Cu-Co-Ni alloy plated plating is as roughening treatment.
Cu-W alloy plated (example 1,2,15,16)
Liquid composition: 15g/ liters of Cu, 100g/ liters of sulfuric acid, 5mg/ liters of W
Temperature: 25 DEG C
(first stage)
Current density (Dk): 90A/dm2
Time: 1.5 seconds
(second stage)
Current density (Dk): 20A/dm2
Time: 3 seconds
Cu-P alloy plated (example 3,4)
Liquid composition: 30g/ liters of Cu, 100g/ liters of sulfuric acid, 500mg/ liters of P
Temperature: 30 DEG C
(first stage)
Current density (Dk): 140A/dm2
Time: 0.6 second
(second stage)
Current density (Dk): 20A/dm2
Time: 2.0 seconds
Cu-Co-Ni alloy plated (example 5,6,14)
Liquid composition: 15g/ liters of Cu, 8g/ liters of Co, 8g/ liters of Ni
PH:1~3
Temperature: 40 DEG C
(first stage)
Current density (Dk): 45A/dm2
Time: 0.6 second
(second stage)
Current density (Dk): 30A/dm2
Time: 0.8 second
Then, sequentially carry out resistance to heat treatment selected from the following, antirust treatment, chromic acid salt treatment, in silane coupling processing At least one above processing.The water that surface is carried out before carrying out each processing is cleaned.
Resistance to heat treatment (forming refractory layer)
Liquid composition: 1~8g/ liters of Co, 10~20g/ liters of Ni
PH:2~3
Temperature: 40 DEG C
Current density (Dk): 5A/dm2
Time: 1.0 seconds
Antirust treatment (forms antirust coat)
Liquid composition: 15~30g/ liters of Ni, 1~10g/ liters of Zn
PH:2~4
Temperature: 40 DEG C
Current density (Dk): 5A/dm2
Time: 1.0 seconds
Electrolytic chromate processing (forms chromating layer)
Liquid composition: K2Cr2O7: 1~10g/ liters, Zn:0~5g/ liters
PH:2~4
Temperature: 40 DEG C
Current density (Dk): 1A/dm2
Time: 1.0 seconds
Silane coupling processing (forms silane and is coupled process layer)
By processed surface spray 1.0 volume % 3- glycidoxypropyltrime,hoxysilane aqueous solution and into After row silane coupling agent coating process, drying in 2 seconds or more is carried out in 70 DEG C or more 200 DEG C of environment below, to go Except the moisture on surface.
Resin layer (example 13,14,15)
The coating of resin layer is used after presclerotic resin is coated on very thin layers of copper side surface using gravure coating process The thickness of resin coating film is adjusted to 10 μm by scraper, in 200 DEG C of dry environment on one side make solvent volatilize while make resin at Divide hardening.Furthermore used resin is using epoxy resin (bisphenol A type epoxy resin of DIC limited liability company manufacture).
Furthermore in example 16, above-mentioned roughening treatment (Cu- also is carried out for the carrier surface of opposite side to very thin layers of copper side W alloy plating), refractory layer, antirust coat, chromating layer, silane coupling process layer surface treatment.
Heat treatment-
Then, following heat treatment are carried out as heat treatment to each Copper foil with carrier: with 99.9% or more Under the nitrogen environment of purity, heated using condition documented by table 2~4.The heating rate of table 2~4 is to first Heating rate in secondary arrival heat treatment condition until documented temperature (heating temperature).After heat treatment until room temperature Cooling time is 1~6 hour.
Also, about example 1~16 being involved in Copper foil with carrier to hollow tube (the outer diameter 11cm, thickness of stainless steel Heated in the state of in 0.5cm).
Also, about example 1~16, be tension when will be involved in the hollow tube be set to setting documented by table 2~4 and into Row heat treatment.
Also, the rotation speed of the hollow tube is set to set documented by table 2~4 and is heated.
2. the evaluation of Copper foil with carrier
For example 1~16 obtained in the above described manner Copper foil with carrier before heat treatment and after heat treatment respectively into Row evaluation test below.Show the results of the evaluation table 2~4.Furthermore the number about the experimental example after the heating of table 2~4 It records, for example, " example 1-1 "~" example 1-50 " is to indicate the sample after respectively being heated the sample before heating i.e. " example 1 ".
The wettability evaluation-of etching solution
In the horizontal plane with the surface-treated layer of ultrathin copper foil side mode above come place Copper foil with carrier (in addition to tool Other than standby resin layer person), 30 μ L, which are added dropwise, at a position using pipette has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight The etching solution of the composition of % (remainder is water) is measured, wipes etching solution after placing 30 seconds.Since Sulfuric-acid-hydrogen-peroxide system loses Carve liquid can on one side the very thin layers of copper for dissolving surface-treated layer and its substrate and while make wetting become larger, if therefore can determine whether as drop Trace close to the etching solution near positive round then surface wetability it is uniform, be then uneven if ellipse.Also, the trace of drop The wetting of the bigger then etching solution of the maximum gauge of mark better, can say it is good using the removal of etching solution.
Soak uniformity
Herein, the maximum gauge and minimum diameter of the trace of drop are measured, if the difference of maximum gauge and minimum diameter exists 10mm hereinafter, the wetability for being then evaluated as etching solution is visibly homogeneous (table 2~4: soaking the column "○" of uniformity), if 5mm with Under, then it is evaluated as further uniformly (table 2~4: soaking the column " ◎ " of uniformity).Also, the maximum in the trace of drop is straight When the difference of the diameter and minimum diameter situation bigger than 10mm, it is evaluated as etching solution wetability not enough uniformly (table 2~4: wetting uniformity Column "×").Herein, " wetting uniformity is maximum-minimum " of table 2~4 is to utilize " the maximum gauge of the trace of drop (mm) minimum diameter (mm) of-drop trace " calculates.
Wetability
The maximum gauge of the trace of drop is measured, if maximum gauge is 25mm or more, it is enough to be evaluated as etching solution wetability Well (table 2~4: the column "○" of wetability) is then evaluated as more preferably good (table 2~4: wetability if 35mm or more Column " ◎ ").Also, not reaching the situation of 25mm in maximum gauge, it is evaluated as the insufficient (table 2~4: the column of wetability of etching solution wetability "×").Herein, " the wetability maximum gauge " of table 2~4 is set to " maximum gauge (mm) of the trace of drop ".
Furthermore in the evaluation of above-mentioned " wetting uniformity " with " wetability ", the circle of the trace of drop will be surrounded Minimum diameter is set as " maximum gauge of the trace of drop ", and the maximum gauge of circle contained in the trace by drop is set as " liquid The minimum diameter of the trace of drop ".
The evaluation-of the tensile strength of carrier
Measure the tensile strength of the carrier measured at normal temperature after heat treatment step in the following manner.
Firstly, removing carrier to obtained Copper foil with carrier.Then, it according to JIS Z 2241 and is utilized for the carrier Tension test acquires tensile strength (tensile strength).
The evaluation-of circuit straight line (circuit formative)
The ultrathin copper foil side of Copper foil with carrier is fitted in double maleimide cyanate resin preimpregnation by thermo-compression bonding After body, removes carrier and remove it, then, the very thin layers of copper surface in a manner of L/S=21 μm/9 μm in exposing forms width The pattern copper plate (thickness of very thin layers of copper and pattern copper plate adds up to 16.5 μm) of 21 μm of degree, then come, pass through erosion below Quarter condition, to pattern copper plate carry out fast-etching until be formed as circuit upper end width be 12~15 μm copper plate to Form circuit.Then, as shown in Figure 5, the maximum value and minimum of the width of the circuit lower end observed above circuit are measured The difference (μm) of value finds out average value obtained by 5 positions of measurement.If maxima and minima difference at 2 μm hereinafter, if be judged as With good circuit linearity, it is evaluated as ◎.Also, when the difference of the maxima and minima is more than 2 μm and when at 4 μm or less, Then it is evaluated as 〇.Also, be evaluated as when the difference of the maxima and minima is more than 4 μm ×.
(etching condition)
Etching form: spraying etching
Nozzle: solid pyramid type
It sprays: 0.10MPa
Etching solution temperature: 30 DEG C
Etching solution composition:
H2O2 18g/L
H2SO4 92g/L
Cu 8g/L
Additive: the FE-830IIW3C of JCU limited liability company manufacture is appropriate
The observation-of gauffer
Very thin layers of copper surface after visually observing the heat treatment of each experimental example has non-wrinkled under the range of length 5m.It can When the position for confirming the gauffer of length 10cm or more is 0 position, it is evaluated as ◎, is evaluated as 〇 when being 1 position, is 2 △ is evaluated as when position, be evaluated as when to be more than 3 positions ×.
Degree of oxidation-
For each experimental example, after a heating treatment, volume 1 is wound off, to the sample that the length of volume 2 is 1m visually to carry out Observation.At this point, discoloration area caused by oxidation is that 5% or less person is evaluated as ◎, aoxidizing caused discoloration area is more than 5% And person is evaluated as 00 below 10%, aoxidize caused by discoloration area be more than 10% and person is evaluated as 〇 below 15%, Discoloration area caused by oxidation is more than 15% and person is evaluated as △ below 20%, aoxidizes caused discoloration area and is more than 20% be evaluated as ×.
By experimental condition and evaluation result is shown in table 1~4.
(evaluation result)
Example 1-1~example 1-48, example 2-1~example 2-3, example 3-5~example 3-13, example 4-1~example 16-1 its circuit Linearity (circuit formative) is all good.About 1~example of example 4,7~example of example 10,14~example of example 16, it is thus understood that: heating Although preceding circuit linearity (circuit formative) is bad, by heat treatment appropriate, (circuit is formed circuit linearity Property) be enhanced.
Furthermore about example 1-1~example 1-48, example 2-1~example 2-6, example 3-5~example 3-13, example 4-1~example 8- 1, example 11-1 and example 16-1, the wetability of etching solution are also all good.
The temperature of its heat treatment of example 1-49 is low, and circuit linearity (circuit formative) is bad.
The time of its heat treatment of example 1-50 is short, and circuit linearity (circuit formative) is bad.
The time of its heat treatment of example 2-4 is long, and coarse grains cause circuit linearity (circuit formative) to become not It is good.
The temperature of its heat treatment of example 2-5 and 2-6 is high, and coarse grains cause circuit linearity (circuit formative) to become It obtains bad.
The heating rate of its heat treatment of example 3-1~example 3-4 is small, and circuit linearity (circuit formative) is bad.

Claims (51)

1. a kind of manufacturing method of Copper foil with carrier, it includes following heat treatment steps: to sequentially have carrier, middle layer, Very thin layers of copper, the Copper foil with carrier of surface-treated layer comprising silane coupling process layer, carry out 1 hour~8 hours heating temperature Degree is 100 DEG C~220 DEG C of heat treatment, and the tensile strength of carrier measured at normal temperature is after above-mentioned heat treatment step 300MPa or more.
2. the manufacturing method of Copper foil with carrier according to claim 1, above-mentioned heat treatment is to add for 1 hour~6 hours The heat treatment that hot temperature is 100 DEG C~220 DEG C.
3. the manufacturing method of Copper foil with carrier according to claim 1, above-mentioned heat treatment is to add for 2 hours~4 hours The heat treatment that hot temperature is 160 DEG C~220 DEG C.
4. a kind of manufacturing method of Copper foil with carrier, it includes following heat treatment steps: to sequentially have carrier, middle layer, Very thin layers of copper, the Copper foil with carrier of surface-treated layer, by reach heating temperature until heating rate be set as more than 50 DEG C/it is small When, 1 hour~8 hours heating temperatures are carried out as 100 DEG C~220 DEG C of heat treatment.
5. the manufacturing method of Copper foil with carrier according to claim 4, above-mentioned heat treatment is to add for 1 hour~6 hours The heat treatment that hot temperature is 100 DEG C~220 DEG C.
6. the manufacturing method of Copper foil with carrier according to claim 4, above-mentioned heat treatment is to add for 2 hours~4 hours The heat treatment that hot temperature is 160 DEG C~220 DEG C.
7. the manufacturing method of Copper foil with carrier according to claim 4, wherein the above-mentioned heating speed in above-mentioned heat treatment Degree is 200 DEG C/h or less.
8. the manufacturing method of Copper foil with carrier according to claim 4, wherein after above-mentioned heat treatment step at normal temperature The tensile strength of measured carrier is 300MPa or more.
9. the manufacturing method of Copper foil with carrier according to claim 7, wherein after above-mentioned heat treatment step at normal temperature The tensile strength of measured carrier is 300MPa or more.
10. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein in above-mentioned heat treatment It in step, is heated under non-reactive gas ambient.
11. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein in above-mentioned heat treatment In step, heat in the state of being involved in Copper foil with carrier into metal hollow tube.
12. the manufacturing method of Copper foil with carrier according to claim 11, wherein, will in above-mentioned heat treatment step Tension when Copper foil with carrier is involved in into metal hollow tube is set as 5~100kgf/m to be heated.
13. the manufacturing method of Copper foil with carrier according to claim 11, wherein, will in above-mentioned heat treatment step Tension when Copper foil with carrier is involved in into metal hollow tube is set as 20~100kgf/m to be heated.
14. the manufacturing method of Copper foil with carrier according to claim 11, wherein in above-mentioned heat treatment step, In the state that Copper foil with carrier is involved in into metal hollow tube, on one side with the rotation of 0.01~600 rotation/hour speed Above-mentioned hollow tube is heated on one side.
15. the manufacturing method of Copper foil with carrier according to claim 12 or 13, wherein in above-mentioned heat treatment step In, in the state of being involved in Copper foil with carrier into metal hollow tube, on one side with 0.01~600 rotation/hour speed Degree rotates above-mentioned hollow tube and is heated on one side.
16. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein before above-mentioned heat treatment Copper foil with carrier further sequentially have middle layer, very thin layers of copper on the surface of above-mentioned carrier side.
17. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein before above-mentioned heat treatment Copper foil with carrier further the surface of above-mentioned carrier side have surface-treated layer.
18. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein above-mentioned surface-treated layer Include roughening treatment layer.
19. the manufacturing method of Copper foil with carrier according to claim 18, wherein at above-mentioned surface-treated layer is roughening The surface of reason layer, which further has to be selected from, is coupled what process layer was constituted by refractory layer, antirust coat, chromating layer and silane The layer of one or more of group.
20. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein before above-mentioned heat treatment Copper foil with carrier have on the surface of above-mentioned very thin layers of copper selected from by roughening treatment layer, refractory layer, antirust coat, chromic acid salt treatment One layer or more of layer in group composed by layer and silane coupling process layer is as surface-treated layer.
21. the manufacturing method of Copper foil with carrier according to any one of claim 1 to 9, wherein before above-mentioned heat treatment Copper foil with carrier have resin layer on above-mentioned surface-treated layer.
22. a kind of manufacturing method of copper-cover laminated plate, using has through appendix body described in any one of claim 1 to 21 Copper foil with carrier obtained by the manufacturing method of copper foil.
23. a kind of manufacturing method of printing distributing board, using has through appendix body described in any one of claim 1 to 21 Copper foil with carrier obtained by the manufacturing method of copper foil.
24. a kind of manufacturing method of printing distributing board, it includes following steps:
It is ready to pass through Copper foil with carrier obtained by the manufacturing method of Copper foil with carrier described in any one of claim 1 to 21 With insulating substrate；
By above-mentioned Copper foil with carrier and insulating substrate lamination；And
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the shape through the step of removing the carrier of above-mentioned Copper foil with carrier At copper-cover laminated plate,
Thereafter, circuit is formed by method either in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
25. a kind of manufacturing method of printing distributing board, it includes following steps:
The Copper foil with carrier obtained by the manufacturing method by Copper foil with carrier described in any one of claim 1 to 21 Above-mentioned very thin layers of copper side surface forms circuit；
Above-mentioned very thin layers of copper side surface in a manner of burying foregoing circuit in above-mentioned Copper foil with carrier forms resin layer；
Circuit is formed on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, above-mentioned carrier is removed；And
After removing above-mentioned carrier, above-mentioned very thin layers of copper is removed, thus makes to be formed in being buried in for above-mentioned very thin layers of copper side surface The circuit of above-mentioned resin layer exposes.
26. a kind of manufacturing method of printing distributing board, it includes following steps:
The Copper foil with carrier obtained by the manufacturing method by Copper foil with carrier described in any one of claim 1 to 21 Above-mentioned carrier side circuit forming surface；
Resin layer is formed in the above-mentioned carrier side surface of above-mentioned Copper foil with carrier in a manner of burying foregoing circuit；
Circuit is formed on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, above-mentioned very thin layers of copper is removed；And
After removing above-mentioned very thin layers of copper, above-mentioned carrier is removed, thus makes to be formed in being buried in for above-mentioned carrier side surface above-mentioned The circuit of resin layer exposes.
27. a kind of manufacturing method of e-machine is matched using having by printing described in any one of claim 23 to 26 Printing distributing board obtained by the manufacturing method of line plate.
28. a kind of Copper foil with carrier is the manufacturing method by Copper foil with carrier described in any one of claim 1 to 21 And it is made.
29. a kind of Copper foil with carrier sequentially has carrier, middle layer, very thin layers of copper, the surface comprising silane coupling process layer Process layer places Copper foil with carrier in mode above with the surface-treated layer of ultrathin copper foil side in the horizontal plane, uses suction 30 μ L, which are added dropwise, at a position in buret has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, and remainder is the composition of water Etching solution, after wiping etching solution after placing 30 seconds, the difference of the maximum gauge of the trace of etching solution and minimum diameter be 10mm hereinafter, Also, above-mentioned Copper foil with carrier does not include the person that has resin layer.
30. Copper foil with carrier according to claim 29 sequentially has carrier, middle layer, very thin layers of copper, includes silane It is coupled the surface-treated layer of process layer, it is attached to place in mode above with the surface-treated layer of ultrathin copper foil side in the horizontal plane Carrier copper foil, 30 μ L, which are added dropwise, at a position using pipette has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, remaining Part is the etching solution of the composition of water, after wiping etching solution after placing 30 seconds, the maximum gauge of the trace of etching solution be 25mm with On, in addition, above-mentioned Copper foil with carrier does not include the person that has resin layer.
31. a kind of Copper foil with carrier sequentially has carrier, middle layer, very thin layers of copper, the surface comprising silane coupling process layer Process layer places Copper foil with carrier in mode above with the surface-treated layer of ultrathin copper foil side in the horizontal plane, uses suction 30 μ L, which are added dropwise, at a position in buret has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, and remainder is the composition of water Etching solution, after wiping etching solution after placing 30 seconds, the maximum gauge of the trace of etching solution is 25mm or more, in addition, above-mentioned appendix body Copper foil does not include the person that has resin layer.
32. a kind of Copper foil with carrier sequentially has carrier, middle layer, very thin layers of copper, surface-treated layer, in the horizontal plane with The surface-treated layer of ultrathin copper foil side places Copper foil with carrier in mode above, is added dropwise 30 at a position using pipette μ L has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, and remainder is the etching solution of the composition of water, wipes after placing 30 seconds After falling etching solution, the maximum gauge of the trace of etching solution and the difference of minimum diameter are 10mm or less, in addition, above-mentioned Copper foil with carrier is not Including the person that has resin layer.
33. Copper foil with carrier according to claim 32 sequentially has carrier, middle layer, very thin layers of copper, surface treatment Layer places Copper foil with carrier in mode above with the surface-treated layer of ultrathin copper foil side in the horizontal plane, uses pipette 30 μ L, which are added dropwise, at a position has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, and remainder is the etching of the composition of water Liquid, after wiping etching solution after placing 30 seconds, the maximum gauge of the trace of etching solution is 25mm or more, in addition, above-mentioned Copper foil with carrier It does not include the person that has resin layer.
34. a kind of Copper foil with carrier sequentially has carrier, middle layer, very thin layers of copper, surface-treated layer, in the horizontal plane with The surface-treated layer of ultrathin copper foil side places Copper foil with carrier in mode above, is added dropwise 30 at a position using pipette μ L has 24 weight %- hydrogen peroxide of sulfuric acid, 15 weight %, and remainder is the etching solution of the composition of water, wipes after placing 30 seconds After falling etching solution, the maximum gauge of the trace of etching solution is 25mm or more, in addition, above-mentioned Copper foil with carrier does not include having resin layer Person.
35. the Copper foil with carrier according to any one of claim 29 to 34, wherein the maximum of the trace of above-mentioned etching solution The difference of diameter and minimum diameter is 5mm or less.
36. the Copper foil with carrier according to any one of claim 29 to 34, wherein the maximum of the trace of above-mentioned etching solution Diameter is 35mm or more.
37. Copper foil with carrier according to claim 35, wherein the maximum gauge of the trace of above-mentioned etching solution be 35mm with On.
38. a kind of laminate is made using Copper foil with carrier described in any one of claim 28 to 37.
39. a kind of laminate, containing Copper foil with carrier and resin described in any one of claim 28 to 37, above-mentioned appendix Part or all of the end face of body copper foil is covered by above-mentioned resin.
It is by Copper foil with carrier described in any one of claim 28 to 37 from above-mentioned carrier 40. a kind of laminate The Copper foil with carrier of side or above-mentioned surface-treated layer side lamination described in any one of another claim 28 to 37 it is above-mentioned Carrier side or above-mentioned surface-treated layer side form.
41. laminate according to claim 40, wherein the above-mentioned carrier side surface of said one Copper foil with carrier or on State above-mentioned carrier side surface or the above-mentioned surface-treated layer side table of surface-treated layer side surface and another above-mentioned Copper foil with carrier Face is optionally configured via the direct lamination of solid.
42. laminate according to claim 40, wherein the above-mentioned carrier of said one Copper foil with carrier or above-mentioned surface Process layer is engaged with the above-mentioned carrier of another above-mentioned Copper foil with carrier or above-mentioned surface-treated layer.
43. laminate according to claim 41, wherein the above-mentioned carrier of said one Copper foil with carrier or above-mentioned surface Process layer is engaged with the above-mentioned carrier of another above-mentioned Copper foil with carrier or above-mentioned surface-treated layer.
44. the laminate according to any one of claim 38 to 43, wherein a part of the end face of above-mentioned laminate or All covered by resin.
45. a kind of printing distributing board is fabricated using Copper foil with carrier described in any one of claim 28 to 37 Person.
46. a kind of e-machine is fabricated using the printing distributing board described in claim 45.
47. a kind of manufacturing method of printing distributing board, it includes following steps:
Prepare Copper foil with carrier and insulating substrate described in any one of claim 28 to 37；
By above-mentioned Copper foil with carrier and insulating substrate lamination；And
After by above-mentioned Copper foil with carrier and insulating substrate lamination, the shape through the step of removing the carrier of above-mentioned Copper foil with carrier At copper-cover laminated plate,
Thereafter, circuit is formed by method either in semi-additive process, subtractive process, part addition process or improvement semi-additive process.
48. a kind of manufacturing method of printing distributing board, it includes following steps:
The above-mentioned very thin layers of copper side surface of Copper foil with carrier described in any one of claim 28 to 37 or above-mentioned carrier side Circuit forming surface；
In the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier or above-mentioned carrier side surface in a manner of burying foregoing circuit Form resin layer；
After forming above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed；And
After removing above-mentioned carrier or above-mentioned very thin layers of copper, above-mentioned very thin layers of copper or above-mentioned carrier are removed, thus makes to be formed in The circuit for being buried in above-mentioned resin layer for stating very thin layers of copper side surface or above-mentioned carrier side surface exposes.
49. a kind of manufacturing method of printing distributing board, it includes following steps:
The above-mentioned very thin layers of copper side surface of Copper foil with carrier described in any one of claim 28 to 37 or above-mentioned carrier side Circuit forming surface；
In the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier or above-mentioned carrier side surface in a manner of burying foregoing circuit Form resin layer；
Circuit is formed on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, above-mentioned carrier or above-mentioned very thin layers of copper are removed；And
After removing above-mentioned carrier or above-mentioned very thin layers of copper, above-mentioned very thin layers of copper or above-mentioned carrier are removed, thus makes to be formed in The circuit for being buried in above-mentioned resin layer for stating very thin layers of copper side surface or above-mentioned carrier side surface exposes.
50. a kind of manufacturing method of printing distributing board, it includes following steps:
By the above-mentioned very thin layers of copper side surface of Copper foil with carrier described in any one of claim 28 to 37 and resin substrate into Row lamination；
There is the side of resin substrate to be at least arranged 1 time for the above-mentioned carrier side surface of opposite side in the lamination with above-mentioned Copper foil with carrier This two layers of resin layer and circuit；And
After forming this two layers of above-mentioned resin layer and circuit, above-mentioned carrier is removed from above-mentioned Copper foil with carrier.
51. a kind of manufacturing method of printing distributing board, it includes following steps:
The above-mentioned carrier side surface of Copper foil with carrier described in any one of claim 28 to 37 is accumulated with resin substrate Layer；
There is the side of resin substrate to be at least arranged 1 time for the very thin layers of copper side surface of opposite side in the lamination with above-mentioned Copper foil with carrier This two layers of resin layer and circuit；And
After forming this two layers of above-mentioned resin layer and circuit, above-mentioned very thin layers of copper is removed from above-mentioned Copper foil with carrier.
CN201510535361.0A 2014-08-29 2015-08-27 Preparation method, the preparation method of copper-cover laminated plate, the preparation method of printing distributing board, the preparation method of e-machine and their product of Copper foil with carrier Active CN105392297B (en)

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