CN108277513A - The copper foil of appendix body, the manufacturing method of copper-cover laminated plate, printed circuit board, e-machine and printed circuit board - Google Patents
The copper foil of appendix body, the manufacturing method of copper-cover laminated plate, printed circuit board, e-machine and printed circuit board Download PDFInfo
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- CN108277513A CN108277513A CN201810174503.9A CN201810174503A CN108277513A CN 108277513 A CN108277513 A CN 108277513A CN 201810174503 A CN201810174503 A CN 201810174503A CN 108277513 A CN108277513 A CN 108277513A
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- China
- Prior art keywords
- copper
- layer
- copper foil
- thin layers
- appendix body
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
- H05K3/242—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus characterised by using temporary conductors on the printed circuit for electrically connecting areas which are to be electroplated
Abstract
The present invention relates to the manufacturing methods of the copper foil of appendix body, copper-cover laminated plate, printed circuit board, e-machine and printed circuit board, provide a kind of copper foil of appendix body that realizing good visibility and machining accuracy.The present invention is a kind of copper foil of appendix body, sequentially has carrier, middle layer and very thin layers of copper, and the aberration Δ L based on JISZ8730 on above-mentioned very thin layers of copper surface is 40 or less.
Description
The present invention is that Chinese Patent Application No. is 201480011096.X, and entitled " copper foil of appendix body covers copper product
The manufacturing method of laminate, printed circuit board, e-machine and printed circuit board ", the entrance that the applying date is on 06 13rd, 2014
The divisional application of the PCT Patent Application of China.
Technical field
The present invention relates to a kind of copper foil, copper-cover laminated plate, printed circuit board, e-machine and the printed circuits of appendix body
The manufacturing method of plate.
Background technology
For in terms of the easiness of wiring or light weight, the miniature electric machines such as Smartphone or tablet PC are using soft
Property printed circuit board (being denoted as FPC below).In recent years, required because of the multifunction of these e-machines FPC multiple stratification or
Person requires printed circuit board the miniaturization (micro- spacing) of conductive pattern.With such requirement, in forming circuit on wiring
Coating is representative, and carrying out the good processing of precision in specific position becomes even more important.
On the other hand, micro- spacing is coped with, requires 5 μm of copper foils below of 9 μm of thickness or less and then thickness, but this recently
The mechanical strength of the very thin copper foil of kind is relatively low, is easily broken or generates gauffer when manufacturing printed circuit board, therefore occur
Using the metal foil with thickness as carrier, the copper foil of appendix body made of very thin layers of copper is electroplated via peeling layer thereon.
In the surface of very thin layers of copper is fitted in insulating substrate after being thermally compressed, carrier is removed via peeling layer and is removed.Pass through
After utilizing resist to form circuit pattern in the very thin layers of copper of exposing, using Sulfuric-acid-hydrogen-peroxide system etchant by very thin copper
Method (the MSAP of layer etching removal：Modified-Semi-Additive-Process improves semi-additive process) and formed fine
Circuit.The technology of copper foil as the appendix body about such fine circuits purposes, such as can enumerate：No. WO2004/005588
(patent document 1), Japanese Unexamined Patent Publication 2007-007937 bulletins (patent document 2), Japanese Patent Laid-Open 2010-006071 public affairs
Report (patent document 3) and Japanese Patent Laid-Open 2009-004423 bulletins (patent document 4) etc..
[patent document 1] No. WO2004/005588 number
[patent document 2] Japanese Unexamined Patent Publication 2007-007937 bulletins
[patent document 3] Japanese Unexamined Patent Publication 2010-006071 bulletins
[patent document 4] Japanese Unexamined Patent Publication 2009-004423 bulletins.
Invention content
[the invention project to be solved]
In the exploitation of the copper foil of appendix body, center of gravity is placed in the stripping for ensuring very thin layers of copper and resin base material so far
Intensity.It is not yet adequately studied accordingly, with respect to micro- spacingization, the technology of the raising about resulting machining accuracy is still
There is room for improvement.Therefore, the issue of the present invention is to provide a kind of copper foils of appendix body that realizing good machining accuracy.
Effort research is repeated in present inventor et al., as a result, it has been found that can provide a kind of by controlling the copper foil of appendix body
The aberration Δ L based on JISZ8730 on the specific aberration of very thin layers of copper, specifically very thin layers of copper surface, and realize good
The copper foil of the appendix body of machining accuracy.
The present invention completed based on the above opinion is a kind of copper foil of appendix body in one side, sequentially has and carries
Body, middle layer and very thin layers of copper, and the aberration Δ L based on JISZ8730 on above-mentioned very thin layers of copper surface is -40 or less.
The present invention is a kind of copper foil of appendix body in another aspect, sequentially has carrier, middle layer and very thin copper
Layer, and the aberration Δ E*ab based on JISZ8730 on above-mentioned very thin layers of copper surface is 45 or more.
The copper foil of the appendix body of the present invention is in an embodiment, the color based on JISZ8730 on above-mentioned very thin layers of copper surface
Poor Δ a is 20 or less.
The present invention appendix body copper foil in another embodiment, above-mentioned very thin layers of copper surface based on JISZ8730's
Aberration Δ b is 20 or less.
For the copper foil of the appendix body of the present invention in another embodiment, above-mentioned middle layer contains Ni,
By the copper foil of above-mentioned appendix body after 220 DEG C are heated 2 hours, above-mentioned very thin layers of copper is removed according to JIS C 6471
When, the Ni adhesion amounts of the above-mentioned middle layer side surface of above-mentioned very thin layers of copper are 5 μ g/dm2The above 300 μ g/dm2Below.
The copper foil of the appendix body of the present invention is small in 220 DEG C of heating 2 by the copper foil of above-mentioned appendix body in another embodiment
Shi Hou, when removing above-mentioned very thin layers of copper, the Ni adhesion amounts of the above-mentioned middle layer side surface of above-mentioned very thin layers of copper are 5 μ g/dm2With
Upper 250 μ g/dm2Below.
The copper foil of the appendix body of the present invention is small in 220 DEG C of heating 2 by the copper foil of above-mentioned appendix body in another embodiment
Shi Hou, when removing above-mentioned very thin layers of copper, the Ni adhesion amounts of the above-mentioned middle layer side surface of above-mentioned very thin layers of copper are 5 μ g/dm2With
Upper 200 μ g/dm2Below.
The copper foil of the appendix body of the present invention is small in 220 DEG C of heating 2 by the copper foil of above-mentioned appendix body in another embodiment
Shi Hou, when removing above-mentioned very thin layers of copper, the Ni adhesion amounts of the above-mentioned middle layer side surface of above-mentioned very thin layers of copper are 5 μ g/dm2With
Upper 150 μ g/dm2Below.
The copper foil of the appendix body of the present invention is small in 220 DEG C of heating 2 by the copper foil of above-mentioned appendix body in another embodiment
Shi Hou, when removing above-mentioned very thin layers of copper, the Ni adhesion amounts of the above-mentioned middle layer side surface of above-mentioned very thin layers of copper are 5 μ g/dm2With
Upper 100 μ g/dm2Below.
For the copper foil of the appendix body of the present invention in another embodiment, the Ni contents of above-mentioned middle layer are 100 μ g/dm2With
Upper 5000 μ g/dm2Below.
The present invention appendix body copper foil in another embodiment, above-mentioned middle layer contain selected from by Cr, Ni, Co, Fe,
In the group that Mo, Ti, W, P, Cu, Al, Zn, these alloy, these hydrate, these oxide, organic matter are formed
It is one or more kinds of.
The copper foil of the appendix body of the present invention when above-mentioned middle layer contains the situation of Cr, contains in another embodiment
5~100 μ g/dm of Cr2, when situation containing Mo, contain 50 μ g/dm of Mo2The above 1000 μ g/dm2Hereinafter, in containing Zn's
When situation, contain 1 μ g/dm of Zn2The above 120 μ g/dm2Below.
For the copper foil of the appendix body of the present invention in another embodiment, it is 25nm or more 80nm that above-mentioned middle layer, which contains thickness,
Organic matter below.
For the copper foil of the appendix body of the present invention in another embodiment, above-mentioned organic matter is by selected from nitrogenous organic compound
The organic matter of object, the organic compound of sulfur-bearing and the one kind or two or more composition in carboxylic acid.
The copper foil of the appendix body of the present invention is coarse using contact pin type according to JIS B0601-1982 in another embodiment
The surface roughness Rz for spending the above-mentioned very thin layers of copper surface measured is 0.2 μm or more 1.5 μm or less.
The copper foil of the appendix body of the present invention is coarse using contact pin type according to JIS B0601-1982 in another embodiment
The surface roughness Rz for spending the above-mentioned very thin layers of copper surface measured is 0.2 μm or more 1.0 μm or less.
The copper foil of the appendix body of the present invention is coarse using contact pin type according to JIS B0601-1982 in another embodiment
The surface roughness Rz for spending the above-mentioned very thin layers of copper surface measured is 0.2 μm or more 0.6 μm or less.
For the copper foil of the appendix body of the present invention in another embodiment, the standard deviation of above-mentioned surface roughness Rz is 0.6 μ
M or less.
For the copper foil of the appendix body of the present invention in another embodiment, the standard deviation of above-mentioned surface roughness Rz is 0.4 μ
M or less.
For the copper foil of the appendix body of the present invention in another embodiment, the standard deviation of above-mentioned surface roughness Rz is 0.2 μ
M or less.
For the copper foil of the appendix body of the present invention in another embodiment, the standard deviation of above-mentioned surface roughness Rz is 0.1 μ
M or less.
Insulating substrate is attached at above-mentioned by the copper foil of the appendix body of the present invention in another embodiment under normal temperature and pressure
Behind the very thin layers of copper side surface of the copper foil of appendix body, and/or
By in air, in 20kgf/cm2Pressure under carry out 220 DEG C × 2 hours heating and by insulating substrate heat
After being crimped on the very thin layers of copper side surface of the copper foil of above-mentioned appendix body, and/or
By in air, in 20kgf/cm2Pressure under carry out 220 DEG C × 2 hours heating and by insulating substrate heat
After being crimped on the very thin layers of copper side surface of the copper foil of above-mentioned appendix body, carried out 2 times 180 DEG C × 1 in nitrogen atmosphere, under normal pressure
After the heating of hour, in the state of through thermo-compression bonding,
Peel strength when removing above-mentioned very thin layers of copper according to JIS C 6471 is 2~100N/m.
For the copper foil of the appendix body of the present invention in another embodiment, above-mentioned peel strength is 2~50N/m.
For the copper foil of the appendix body of the present invention in another embodiment, above-mentioned peel strength is 2~20N/m.
The copper foil of the appendix body of the present invention sequentially has among the above in another embodiment in two faces of above-mentioned carrier
Interbed and above-mentioned very thin layers of copper.
For the copper foil of the appendix body of the present invention in another embodiment, above-mentioned carrier is by electrolytic copper foil or rolled copper foil shape
At.
The copper foil of the appendix body of the present invention is in another embodiment, at least the one of above-mentioned very thin layers of copper and above-mentioned carrier
A surface or two surfaces have roughening treatment layer.
The present invention appendix body copper foil in another embodiment, above-mentioned roughening treatment layer be by be selected from by copper, nickel,
The simple substance of any one of the group that cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc are formed or the layer constituted containing wantonly a kind or more of alloy.
The present invention appendix body copper foil in another embodiment, in the surface of above-mentioned roughening treatment layer have selected from by
The layer of one or more of the group that refractory layer, antirust coat, chromating layer and silane coupling process layer are formed.
The copper foil of the appendix body of the present invention is in another embodiment, at least the one of above-mentioned very thin layers of copper and above-mentioned carrier
A surface or two surfaces have to be selected from is coupled what process layer was formed by refractory layer, antirust coat, chromating layer and silane
The layer of one or more of group.
The copper foil of the appendix body of the present invention is in another embodiment, in a surface of above-mentioned very thin layers of copper or two tables
Face has in the group being made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer
1 kind or more of layer.
The copper foil of the appendix body of the present invention is in another embodiment, in having resin layer in above-mentioned very thin layers of copper.
The copper foil of the appendix body of the present invention is in another embodiment, in having resin layer on above-mentioned roughening treatment layer.
The copper foil of the appendix body of the present invention is in another embodiment, in above-mentioned selected from by refractory layer, antirust coat, chromate
Has resin layer on the layer of one or more of the group that process layer and silane coupling process layer are formed.
The present invention is a kind of copper-cover laminated plate in another aspect, is manufactured using the copper foil of the appendix body of the present invention.
The present invention is a kind of printed circuit board in another aspect, is manufactured using the copper foil of the appendix body of the present invention.
The present invention is a kind of e-machine in another aspect, is manufactured using the printed circuit board of the present invention.
The present invention is a kind of manufacturing method of printed circuit board in another aspect, contains and has the following steps：Prepare this hair
The step of copper foil and insulating substrate of bright appendix body；The step of by the copper foil of above-mentioned appendix body and insulating substrate lamination；And in
After the copper foil of above-mentioned appendix body and insulating substrate lamination, by the step of foil carriers of the copper foil of above-mentioned appendix body are removed
And copper-cover laminated plate is formed, thereafter, pass through any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process
Method forms the step of circuit.
The present invention is a kind of manufacturing method of printed circuit board in another aspect, contains and has the following steps：In the present invention
The above-mentioned very thin layers of copper side surface of copper foil of appendix body the step of forming circuit；In above-mentioned attached in a manner of burying foregoing circuit
The step of above-mentioned very thin layers of copper side surface of the copper foil of carrier forms resin layer；In the step of forming circuit on above-mentioned resin layer；
After forming circuit on above-mentioned resin layer, the step of removing above-mentioned carrier；And by removing above-mentioned pole after removing above-mentioned carrier
Thin copper layer, and the step of making the circuit for being buried in above-mentioned resin layer for being formed in above-mentioned very thin layers of copper side surface expose.
The manufacturing method of the printed circuit board of the present invention is in an embodiment, in the step for forming circuit on above-mentioned resin layer
Suddenly it is to fit in the copper foil of another appendix body on above-mentioned resin layer from very thin layers of copper side, using fitting in the attached of above-mentioned resin layer
The copper foil of carrier and the step of form foregoing circuit.
The manufacturing method of the printed circuit board of the present invention fits in another on above-mentioned resin layer in another embodiment
The copper foil of appendix body is the copper foil of the appendix body of the present invention.
The manufacturing method of the printed circuit board of the present invention is in another embodiment, in formation circuit on above-mentioned resin layer
Step is carried out by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method.
The manufacturing method of the printed circuit board of the present invention contains in another embodiment before removing carrier, in
The carrier side surface of the copper foil of appendix body forms the step of substrate.
According to the present invention, it is possible to provide a kind of copper foil of appendix body that realizing good visibility and machining accuracy.
Description of the drawings
A~C of Fig. 1 be using the present invention appendix body copper foil printed circuit board manufacturing method concrete example extremely
The schematic diagram of circuit board section in the step of until plating circuit, removal resist.
D~F of Fig. 2 is oneself of the concrete example of the manufacturing method of the printed circuit board for the copper foil for using the appendix body of the present invention
Resin and the 2nd layer of appendix body it is copper foil laminated until laser opening the step of in circuit board section schematic diagram.
G~I of Fig. 3 is oneself of the concrete example of the manufacturing method of the printed circuit board for the copper foil for using the appendix body of the present invention
Form the schematic diagram of the circuit board section in the step of through-hole filler is until removing the 1st layer of carrier.
J~K of Fig. 4 is oneself of the concrete example of the manufacturing method of the printed circuit board for the copper foil for using the appendix body of the present invention
The schematic diagram of circuit board section in the step of fast-etching is until forming convex block, copper post.
Fig. 5 is the schematic diagram for the fortune foil mode for indicating drum-type.
Fig. 6 is the schematic diagram for the fortune foil mode for indicating that hair clip is curved.
Fig. 7 is the chart for indicating etching period and the relationship of the thickness of reduction due to etching.
Fig. 8 is the measurement site for indicating sample strip in the evaluation using the depth profile for carbon concentration figure of XPS measurement acquisitions
Schematic diagram.
Specific implementation mode
The copper foil ＞ of ＜ appendix bodies
The copper foil of the appendix body of the present invention sequentially has carrier, middle layer and very thin layers of copper.The copper foil of appendix body itself
Application method is well known to those skilled in the art, such as the surface of very thin layers of copper fitted in paper base material phenol resin, paper substrate
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, polyimide film, liquid crystalline polymer film, fluororesin film
On equal insulating substrates, carrier is removed after being thermally compressed, the very thin layers of copper for being attached to insulating substrate is etched to target conductor figure
Case can finally manufacture printed circuit board.
＜ carriers ＞
The carrier that can be used in the present invention is typically metal foil or resin film, such as can be 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, LCD films
Form provide.
It is to be provided in the form of rolled copper foil or electrolytic copper foil for the carrier typical case that can be used in the present invention.In general,
Electrolytic copper foil is that copper is electrolysed to precipitation to manufacture to the rotating cylinder of titanium or stainless steel from copper sulfate bath, and rolled copper foil is to repeat
Manufactured using the plastic processing of stack with being heat-treated.As the material of copper foil, except refined copper (compile by JIS H3100 alloys
Number C1100) or the high-purity coppers such as oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloys number C1011) with
Outside, it also can be used such as mixing Sn copper, mix Ag copper, added with the copper alloy Cr, Zr or Mg, the inferior system of the card added with Ni and Si etc.
The copper alloy of copper alloy etc.
Also, as electrolytic copper foil, made using following electrolyte composition and manufacturing condition.In the following conditions system of utilization
When making the situation of electrolytic copper foil, can get copper foil surface TD (in the manufacturing equipment of copper foil with the direction of travel of copper foil in straight
The direction (width direction) at angle) Rz is small, electrolytic copper foil that TD 60 degree of glossiness are high.
Furthermore used in plating of the manufacture of the copper foil described in this specification, the surface treatment of copper foil or copper foil etc.
Treatment fluid remainder as long as no special instructions, then be water.
＜ electrolyte forms ＞
Copper：90~110g/L
Sulfuric acid：90~110g/L
Chlorine：50~100ppm
Leveling agent 1 (bis- (3- sulfopropyls) disulphide)：10~30ppm
Leveling agent 2 (amine compounds)：10~30ppm
The amine compounds of following below formula can be used in above-mentioned amine compounds.
(in above-mentioned chemical formula, R1And R2Alkyl, unsaturated hydrocarbons are replaced by hydroxy alkyl, ether, aryl, aromatic series to be selected from
Person in the group that base, alkyl are formed)
＜ manufacturing conditions ＞
Current density：70~100A/dm2
Electrolyte temperature：50~60 DEG C
Electrolyte linear velocity：3~5m/sec
Electrolysis time：0.5~10 minute
Also include copper alloy foil furthermore when term " copper foil " in this manual, is used alone.
The thickness for the carrier that can be used in the present invention is also not particularly limited, as long as in terms of realizing the effect as carrier
It is suitably adjusted to suitable thickness, such as 5 μm or more can be set as.But if blocked up, increased production cost, thus it is logical
Often preferably it is set as 35 μm or less.Therefore, the thickness of carrier is typically 8~70 μm, more typically 12~70 μm, more typically 18
~35 μm.Also, for reducing the viewpoint of cost of material, the thickness of carrier is preferred with small.Therefore, the thickness of carrier is typically 5 μ
35 μm of m or more hereinafter, preferably 5 μm or more 18 μm hereinafter, more preferably 5 μm or more 12 μm hereinafter, in turn be preferably 5 μm or more
11 μm hereinafter, be more preferably 5 μm or more 10 μm or less in turn.Furthermore when the thickness of carrier small situation, in the logical foil of carrier
When easy to produce bending.Bending is generated in order to prevent, such as effectively becomes the carrying roller of the copper foil manufacturing device of appendix body
It obtains smoothly, or shortens carrying roller at a distance from next carrying roller.Furthermore in burying for one of manufacturing method as printed circuit board
When entering to use the situation of the copper foil of appendix body in method (embedding inlay technique (Enbedded Process)), the rigidity of carrier must be higher.
Therefore, when the situation for implantation, the thickness of carrier is preferably 18 μm or more 300 μm hereinafter, more preferably 25 μm or more
150 μm hereinafter, in turn be preferably 35 μm or more 100 μm hereinafter, in turn more preferably 35 μm or more 70 μm or less.
＜ middle layers ＞
In middle layer is arranged on carrier.Other layers can be also set between carrier and middle layer.In being used in the present invention
Interbed is not particularly limited as long as being constructed as follows：The very thin layers of copper before the step of copper foil of appendix body is to insulating substrate lamination
It is not easy to remove 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
The middle layer of the copper foil of the appendix body of invention also contain selected from by Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these
One or more of the group that alloy, these hydrate, these oxide, organic matter are formed.Also, middle layer is also
It can be multilayer.Also, middle layer also may be disposed at the two sides of carrier.
Also, for example, middle layer can be constituted in the following way：From carrier side formed by be selected from by Cr, Ni, Co, Fe, Mo,
The single metal layer that a kind of element in the groups of elements that Ti, W, P, Cu, Al, Zn are formed is constituted, or by be selected from by Cr, Ni,
The alloy-layer that the element of one or more of the groups of elements that Co, Fe, Mo, Ti, W, P, Cu, Al, Zn are formed is constituted, in
Formed thereon by selected from one or both of groups of elements being made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn with
On element hydrate or oxide constitute layer.
Also, can be in middle layer of the setting containing Ni on the single or double of carrier.Middle layer on carrier preferably in sequentially accumulating
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 constitute.
Also, preferably in nickel or nickeliferous alloy wantonly a kind of layer and/or containing chromium, evanohm, chromium oxide in wantonly a kind with
On layer in contain zinc.Herein, so-called nickeliferous alloy, refer to by nickel with selected from by cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium,
The alloy that one or more of the group that phosphorus, tungsten, tin, arsenic and titanium are formed element is constituted.Nickeliferous alloy also can be by 3 kinds or more
Element constitute alloy.Also, so-called evanohm, refer to by chromium with selected from by cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten,
The alloy that one or more of the group that tin, arsenic and titanium are formed element is constituted.Evanohm also can be to be made of 3 kinds or more of element
Alloy.Also, containing chromium, evanohm, chromium oxide in wantonly a kind or more of layer also can be chromating layer.Herein, institute
Chromating layer is called, refers to the layer through the liquid processing containing chromic anhybride, chromic acid, two chromic acid, chromate or two chromate.Chromic acid
Salt treatment layer, which can also contain the elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium, (also can be metal, close
Any form such as gold, oxide, nitride, sulfide).As the concrete example of chromating layer, can enumerate：Pure chromium hydrochlorate
Process layer or zinc chromate process layer etc..In the present invention, by the chromic acid salt treatment through chromic anhybride or the processing of two chromic acid aqueous solutions of potassium
Layer is known as pure chromating layer.Also, in the present invention, warp is handled containing chromic anhybride or the treatment fluid of two potassium chromates and zinc
Chromating layer is known as zinc chromate process layer.
Also, middle layer is preferably in sequentially appointing in lamination nickel, nickel-zinc alloy, nickel-phosphor alloy, nickel-cobalt alloy on carrier
1 kind of layer and zinc chromate process layer, pure chromating layer, wantonly a kind of layer in chromium plating layer and constitute, middle layer and then excellent
Be selected as 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 adhesive force of nickel and copper is higher than the adhesive force of chromium and copper,
Therefore when removing very thin layers of copper, become to be removed in the interface of very thin layers of copper and chromating layer.Also, for middle layer
Nickel, expect to prevent copper component from diffusing to the barrier effect of very thin layers of copper from carrier.Also, preferably misaligning interbed carries out chromium plating
It applies and forms chromating layer.Chromium plating lies in surface and forms fine and close chromium oxide layer, therefore in forming pole using plating
When thin copper foil, resistance rises, and easy tos produce pin hole.The surface for being formed with chromating layer is to be formed with compared with chromium plating simultaneously
Unsound chromium oxide layer, therefore it is not easy to become resistance when forming ultrathin copper foil using plating, and pin hole can be reduced.This
Chromating layer is used as by forming zinc chromate process layer in place, and makes to be less than using the resistance being electroplated when forming ultrathin copper foil
Common chromating layer can further suppress the generation of pin hole.
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, in the lamination to insulating substrate
Very thin layers of copper will not be removed from carrier before step, and on the other hand, can get after the layering steps to insulating substrate can will be very thin
The characteristic that layers of copper is removed from carrier, so preferably.Make in nickel layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) are not arranged
When chromating layer is present in carrier and the situation of the boundary of very thin layers of copper, fissility does not almost improve, at chromate-free
Manage 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, with nickel
Nickel amount peel strength in layer or nickeliferous alloy-layer (such as nickel-zinc alloy-layer) is too strong or excessively weak, and can not obtain appropriate
Peel strength.
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 middle layer is also removed therewith when removing very thin layers of copper, i.e., peeling-off between carrier and middle layer, so it is not good enough.
Such situation can not only occur in the case of chromating layer is arranged with the interface of carrier, if in 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 making these contacts, adhesive force 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 interfacial 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 is touched 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
The wet type plating of plating is applied and impregnated, or is formed such as the dry type plating of sputter, CVD and PDV.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 such as can the formation by electrolytic chromate or dipping chromate, but it is dense since chromium can be improved
Degree, makes very thin layers of copper become good from the peel strength of carrier, so preferably formed by electrolytic chromate.
Also, the adhesion amount of the nickel preferably in middle layer is 100~40000 μ g/dm2, the adhesion amount of chromium is 5~100 μ g/
dm2, the adhesion amount of zinc is 1~70 μ g/dm2.As described above, the copper foil control of the appendix body of the present invention is shelled from the copper foil of appendix body
Ni amounts from the very thin layers of copper surface after very thin layers of copper, in order to control the Ni amounts on the very thin layers of copper surface after so stripping, preferably
Contain for middle layer and is reduced the Ni adhesion amounts of middle layer and inhibits metal species (Cr, Zn) of the Ni to very thin layers of copper side diffusion.
For such viewpoint, the Ni contents of middle layer are preferably 100~40000 μ g/dm2, more preferably 200 μ g/dm2Above 20000
μg/dm2Hereinafter, being preferably 500 μ g/dm in turn2The above 10000 μ g/dm2Hereinafter, being more preferably 700 μ g/dm in turn2More than
5000μg/dm2Below.Also, Cr preferably contains 5~100 μ g/dm2, more preferably 8 μ g/dm2The above 50 μ g/dm2Hereinafter, into
And preferably 10 μ g/dm2The above 40 μ g/dm2Hereinafter, being more preferably 12 μ g/dm in turn2The above 30 μ g/dm2Below.Zn is preferably
Contain 1~70 μ g/dm2, more preferably 3 μ g/dm2The above 30 μ g/dm2Hereinafter, being preferably 5 μ g/dm in turn2The above 20 μ g/dm2With
Under.
The middle layer of the copper foil of the appendix body of the present invention is organised in sequentially lamination nickel layer on carrier, and containing nitrogenous
It closes object, the organic compound of sulfur-bearing and the organic matter layer of any one of carboxylic acid and constitutes, the adhesion amount of the nickel in middle layer is also
Can be 100~40000 μ g/dm2.Also, the middle layer of the copper foil of the appendix body of the present invention is in sequentially lamination contains on carrier
The organic compound of nitrogen, the organic matter layer of the organic compound of sulfur-bearing and any one of carboxylic acid and nickel layer and constitute, middle layer
In the adhesion amount of nickel also can be 100~40000 μ g/dm2.As described above, the copper foil of the appendix body of the present invention is controlled from appendix
The copper foil of body removes the Ni amounts on the very thin layers of copper surface after very thin layers of copper, in order to control the very thin layers of copper surface after so stripping
Ni amounts, preferably middle layer contain the Ni adhesion amounts for being reduced middle layer and inhibit Ni to very thin layers of copper side diffusion containing nitrogenous
Organic compound, the organic compound of sulfur-bearing and the organic matter layer of any one of carboxylic acid.For such viewpoint, middle layer
Ni contents be preferably 100~40000 μ g/dm2, more preferably 200 μ g/dm2The above 20000 μ g/dm2Hereinafter, being preferably in turn
300μg/dm2The above 10000 μ g/dm2Hereinafter, being more preferably 500 μ g/dm in turn2The above 5000 μ g/dm2Below.Also, as this
Organic matter containing nitrogenous organic compound, the organic compound of sulfur-bearing and any one of carboxylic acid can enumerate BTA (benzos
Triazole), MBT (mercaptobenzothiazoler) etc..
Also, as the 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 composition 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 for having 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- triazoles and 3- amido -1H-1,2,4- triazoles etc..
The organic compound of sulfur-bearing preferably using mercaptobenzothiazoler, Vencide, trithiocyanuric acid and
2- benzimidazole mercaptans 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 containing thickness be 25nm or more 80nm hereinafter, more preferably containing 30nm or more 70nm with
Under.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 layers
In by the very thin layers of copper of the copper foil of appendix body from carrier stripping after, to the middle layer side table of the very thin layers of copper of exposing
Face, the middle layer side surface progress XPS measurement with the carrier exposed, and depth profile is made.It then, can will be from very thin layers of copper
Middle layer side surface be initially set as A (nm) as 3at% depth below to concentration of carbon, will be from the middle layer side surface of carrier
It initially is set as B (nm) as 3at% depth below to concentration of carbon, 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 devices (ULVAC-PHI companies, model 5600MC)
End 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+, accelerating potential 3kV, scan area 3mm × 3mm, sputtering yield 2.8nm/min (SiO2
Conversion)
About the application method of the organic matter contained by middle layer, 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 in forming middle layer on carrier
In, or the face of middle layer to be formed can be carried out using shower method, spray-on process, dropping method and galvanoplastic etc., without adopting
With the method being particularly limited to.At this point, the concentration of the organic system agent in solvent is in above-mentioned whole organic matters, preferably concentration
The range of 0.01g/L~30g/L, 20~60 DEG C of liquid temperature.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 the solvent for dissolving above-mentioned organic matter
The tactile time is longer, and the organic matter thickness of middle layer is bigger.Also, when the organic matter thickness of middle layer thicker situation, there is suppression
Effect bigger tendencies of the Ni processed to the organic matter of very thin layers of copper side diffusion.
Also, middle layer preferably on carrier sequentially lamination nickel and molybdenum or cobalt or molybdenum-cobalt alloy and constitute.Nickel and copper
Adhesive force, so when removing very thin layers of copper, becomes in very thin layers of copper and molybdenum or cobalt or molybdenum-higher than molybdenum or the adhesive force of cobalt and copper
It is removed at the interface of cobalt alloy.Also, for the nickel of middle layer, the barrier for preventing copper component from diffusing to very thin layers of copper from carrier is expected
Wall effect.
Furthermore above-mentioned nickel also can be nickeliferous alloy.Herein, so-called nickeliferous alloy, refer to by nickel with selected from by cobalt,
The alloy that one or more of the group that iron, chromium, molybdenum, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium are formed element is constituted.Also,
Above-mentioned molybdenum also can be the alloy containing molybdenum.Herein, the so-called alloy containing molybdenum, refer to by molybdenum with selected from by cobalt, iron, chromium, nickel, zinc, tantalum,
The alloy that one or more of the group that copper, aluminium, phosphorus, tungsten, tin, arsenic and titanium are formed element is constituted.Also, above-mentioned cobalt also can be containing cobalt
Alloy.Herein, the so-called alloy containing cobalt, refer to by cobalt with selected from by molybdenum, iron, chromium, nickel, zinc, tantalum, copper, aluminium, phosphorus, tungsten, tin,
The alloy that one or more of the group that arsenic and titanium are formed element is constituted.
Molybdenum-cobalt alloy also contain in addition to molybdenum, cobalt element (such as selected from by cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminium,
The element of one or more of the group that phosphorus, tungsten, tin, arsenic and titanium are formed).
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 molybdenum or cobalt or molybdenum-cobalt alloy layer in middle layer are present in the interface of very thin layers of copper compared with unfertile land, in insulation base
Very thin layers of copper will not be removed from carrier before the layering steps of plate, on the other hand, can get after the layering steps to insulating substrate
The characteristic that very thin layers of copper can be removed from carrier, so preferably.Molybdenum or cobalt or molybdenum-cobalt alloy layer is set to exist in nickel layer is not arranged
When the situation of carrier Yu the boundary of very thin layers of copper, there is the case where fissility does not almost improve, in no molybdenum or cobalt or molybdenum-cobalt alloy
Layer and directly by the situation of nickel layer and very thin layers of copper lamination when, have as the nickel amount peel strength in nickel layer is too strong or excessively weak, and
The case where peel strength appropriate can not be obtained.
Also, if molybdenum or cobalt or molybdenum-cobalt alloy layer are present in the boundary of carrier and nickel layer, there is following situation：In stripping pole
Middle layer is also removed therewith when thin copper layer, i.e., peeling-off between carrier and middle layer, so it is not good enough.Such situation not only in
It can occur in the case that molybdenum or cobalt or molybdenum-cobalt alloy layer are set with the interface of carrier, if in molybdenum is arranged with the interface of very thin layers of copper
Or molybdenum amount or cobalt amount are excessive when cobalt or molybdenum-cobalt alloy layer, then can also occur.Think the reason is that since copper and nickel are easy admittedly
It is molten, if so making these contacts, adhesive force can be improved because of phase counterdiffusion, become to be not easily stripped, on the other hand, due to molybdenum or
Cobalt is not easy to be dissolved with copper, is not susceptible to phase counterdiffusion, so in molybdenum or cobalt or the interfacial adhesion of molybdenum-cobalt alloy layer and copper compared with
It is weak, it is easily peeled off.Also, when the nickel amount insufficient situation of middle layer, there is following situation：It is only deposited between carrier and very thin layers of copper
Micro molybdenum or cobalt, so the two is touched and becomes difficult to remove.
The nickel and cobalt or molybdenum-cobalt alloy of middle layer can for example pass through such as plating, electroless plating and the wet type for impregnating plating
Plating, or formed such as the dry type plating of sputter, CVD and PDV.Also, molybdenum can the only shape by dry type plating of such as CVD and PDV
At.For the viewpoint of cost, preferably it is electroplated.
In middle layer, preferably the adhesion amount of nickel is 100~40000 μ g/dm2, the adhesion amount of molybdenum is 10~1000 μ g/
dm2, the adhesion amount of cobalt is 10~1000 μ g/dm2.As described above, copper foil of the copper foil control of the appendix body of the present invention from appendix body
The Ni amounts for removing the very thin layers of copper surface after very thin layers of copper, it is excellent in order to control the Ni amounts on the very thin layers of copper surface after so stripping
Be selected as middle layer contain be reduced middle layer Ni adhesion amounts and inhibit metal species from Ni to very thin layers of copper side diffusion (Co,
Mo).For such viewpoint, nickel adhesion amount is preferably set as 100~40000 μ g/dm2, more preferably it is set as 200~20000 μ
g/dm2, and then preferably it is set as 300~15000 μ g/dm2, and then more preferably it is set as 300~10000 μ g/dm2.In middle layer
When situation containing molybdenum, molybdenum adhesion amount is preferably set as 10~1000 μ g/dm2, molybdenum adhesion amount is preferably to be set as 20~600 μ g/
dm2, more preferably it is set as 30~400 μ g/dm2.When middle layer contains the situation of cobalt, cobalt adhesion amount is preferably set as 10~
1000μg/dm2, cobalt adhesion amount is preferably to be set as 20~600 μ g/dm2, more preferably it is set as 30~400 μ g/dm2。
Furthermore middle layer is in sequentially lamination has the situation of nickel and molybdenum or cobalt or molybdenum-cobalt alloy on carrier as described above
When, if reducing the conveyance speed for slowing down carrier the current density under the plating processing of molybdenum or cobalt or molybdenum-cobalt alloy layer is arranged
Degree, then have the tendency that molybdenum or cobalt or the density of molybdenum-cobalt alloy layer are got higher.If the density of the layer containing molybdenum and/or cobalt improves, nickel layer
Nickel become to be not easy to spread, can control stripping after very thin layers of copper surface Ni amounts.
When only in the situation of single side setting middle layer, preferably in mutually the antirusts such as Ni plating layers are arranged in face on the contrary with carrier
Layer.Furthermore, it is believed that when using the situation of chromic acid salt treatment or zinc chromate processing or plating processing setting middle layer, there are chromium or zinc
A case where part for the metal of equal attachments becomes hydrate or oxide.
Also, the copper foil of the appendix body of the present invention is preferably when middle layer contains the situation of Ni, heated 2 hours in 220 DEG C
Afterwards, when removing very thin layers of copper according to JIS C 6471, the Ni adhesion amounts of the middle layer side surface of very thin layers of copper are 5 μ g/dm2More than
300μg/dm2Below.After the copper foil of appendix body is fitted in insulating substrate and being thermally compressed, foil carriers are removed, it will be attached
The very thin layers of copper in insulating substrate is etched into target conductor pattern, if at this point, be attached to very thin layers of copper surface (with insulation
The attachment side of substrate mutually on the contrary the surface of side) Ni amounts it is more, then become to be not easy to etch very thin layers of copper, it is difficult to it is electric to form micro- spacing
Road.Therefore, the copper foil of appendix body of the invention is by the Ni adhesion amounts control on the very thin layers of copper surface after stripping as described above
For 300 μ g/dm2Below.If the Ni adhesion amounts are more than 300 μ g/dm2, then be difficult to etch very thin layers of copper and formed compared with L/S=30 μm/
30 μm of finer wirings, such as L/S=25 μm/25 μm of fine wiring, such as L/S=20 μm/20 μm fine are matched
Line, such as L/S=15 μm/15 μm of fine wiring.Furthermore above-mentioned " being heated 2 hours in 220 DEG C " indicates appendix body
Copper foil fit in insulating substrate and be thermally compressed situation when representative heat condition.
If the Ni adhesion amounts on the very thin layers of copper surface after stripping as described above are very few, there is the Cu of foil carriers to very thin
The case where layers of copper side diffusion.When this situation, foil carriers and the combination degree of very thin layers of copper are become too strong, in the very thin copper of stripping
Very thin layers of copper easy tos produce pin hole when layer.Also, there is the case where contiguity power of resin and copper foil deterioration.Therefore, the Ni adhesion amount controls
It is made as 5 μ g/dm2More than.Also, the Ni adhesion amounts are preferably 5 μ g/dm2The above 250 μ g/dm2Hereinafter, more preferably 5 μ g/dm2With
Upper 200 μ g/dm2Below.
Also, as described above, the copper foil of appendix body when removing very thin layers of copper, is there is very thin copper after 220 DEG C are heated 2 hours
The Ni adhesion amounts of the middle layer side surface of layer become 300 μ g/dm2Following situation, in order to control the very thin copper after so stripping
The Ni adhesion amounts of layer surface, middle layer must contain the Ni contents for being reduced middle layer and inhibit Ni to very thin layers of copper side diffusion
Metal species (Cr, Mo, Zn etc.) or organic matter.For such viewpoint, the Ni contents of middle layer are preferably 100 μ g/dm2More than
5000μg/dm2Hereinafter, more preferably 200 μ g/dm2The above 4000 μ g/dm2Hereinafter, being preferably 300 μ g/dm in turn2Above 3000
μg/dm2Hereinafter, being more preferably 400 μ g/dm in turn2The above 2000 μ g/dm2Below.Also, as the metal kind contained by middle layer
Class is preferably selected from by one or more of Cr, Mo, Zn group formed.When situation containing Cr, preferably contain
There are 5~100 μ g/dm of Cr2, more preferably contain 5 μ g/dm2The above 50 μ g/dm2Below.When situation containing Mo, preferably
Contain 50 μ g/dm of Mo2The above 1000 μ g/dm2Hereinafter, more preferably containing 70 μ g/dm2The above 650 μ g/dm2Below.In containing
When the situation of Zn, preferably contain 1 μ g/dm of Zn2The above 120 μ g/dm2Hereinafter, more preferably containing 2 μ g/dm2The above 70 μ g/
dm2Hereinafter, preferably containing 5 μ g/dm in turn2The above 50 μ g/dm2Below.
The very thin layers of copper ＞ of ＜
In very thin layers of copper is arranged in middle layer.Other layers can be also set between middle layer and very thin layers of copper.Very thin layers of copper
It can be formed by using the plating of the electrobath of copper sulphate, cupric pyrophosphate, amidosulfonic acid copper, copper cyanider etc., so that it may Yu Gao electricity
It is formed for the aspect of layers of copper under current density, 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 also may be disposed at the two sides of carrier.Also, can in a surface of very thin layers of copper or
Two surface settings are selected to be made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer
One or more of group layer, surface-treated layer can be also set.Surface-treated layer also can be selected from by roughening treatment layer, heat-resisting
The layer of one or more of the group that layer, antirust coat, chromating layer and silane coupling process layer are formed.
Also, the surface roughness according to the very thin layers of copper surfaces measured using contact pin type roughmeter JIS B0601-1982
Rz (10 mean roughness) is preferably 0.2 μm or more 1.5 μm or less.If coarse using contact pin type according to JIS B0601-1982
The surface roughness Rz on very thin layers of copper surface measured is spent not up to 0.2 μm, then is had in by the copper foil laminated in resin of appendix body
Afterwards, the anxiety that copper foil is removed from resin is led to the problem of when removing carrier from copper foil.If also, being used according to JISB0601-1982 tactile
The surface roughness Rz on the very thin layers of copper surface that pin type roughmeter measures is more than 1.5 μm, then has and generate asking for etching variation
The anxiety of topic.Surface roughness Rz be preferably 0.2 μm or more 1.0 μm hereinafter, more preferably 0.2 μm or more 0.9 μm hereinafter, in turn
Preferably 0.25 μm or more 0.8 μm hereinafter, in turn be more preferably 0.28 μm or more 0.7 μm or less, 0.28 μm or more 0.6 μm with
Under.
Furthermore in order to reduce Rz, effectively reduces the Rz in the directions TD of carrier and improve 60 degree of glossiness.Also, in right
When very thin layers of copper surface carries out the situation of roughening treatment, the current density in roughening treatment is effectively improved, and shorten roughening
Processing time.
The roughness (Rz) and glossiness of the TD of the processing side surface of carrier before control middle layer is formed as follows.
Specifically, the surface roughness (Rz) of TD of the copper foil before surface treatment is preferably 0.20~0.55 μm, more preferably 0.20
~0.42 μm.As such copper foil, it can adjust the oil film equivalent of rolling oil and rolled (high glaze calendering) or adjustment calendering
The surface roughness of roller and rolled (such as when the situation being measured on the direction rectangular with the circumferencial direction of roller,
The arithmetic average roughness Ra for rolling roller surface (JIS B0601) can be set as 0.01~0.25 μm；In the calculation of calendering roller surface
When the larger situation of the value of art average roughness Ra, there is the roughness (Rz) of the TD of copper foil to become larger, the tendency that glossiness reduces；
Also, when the value smaller situation for the arithmetic average roughness Ra for rolling roller surface, there is the roughness (Rz) of the TD of copper foil to become smaller,
The tendency that glossiness improves), or made by the electrolytic polishing in the chemical grinding or phosphoric acid solution of such as chemical etching.Such as
This, is above range by making surface roughness (Rz) and the glossiness of the TD of the copper foil before processing, can easily control process
The surface roughness (Rz) and surface area of copper foil afterwards.
Also, the copper foil before surface treatment be preferably TD 60 degree glossiness for 300~910%, more preferably 500~
810%, and then preferably 500~710%.If 60 degree of glossiness of the MD of the copper foil before surface treatment not up to 300%, with
300% or more situation is compared, and has the hyalinosis of above-mentioned resin to obtain undesirable anxiety, if more than 910%, has generation to become difficult
The anxiety of the problem of to be manufactured.
Furthermore high glaze calendering can by oil film equivalent as defined in following formula is set as 10000~24000 or less into
Row.
Oil film equivalent={ (calendering oil viscosity [cSt]) × (plate speed [mpm]+roller circular velocity [mpm]) }/{ (roller is nibbled
Close angle [rad]) × (yield stress [kg/mm of material2])}
It is in 40 DEG C of kinetic viscosity to roll oil viscosity [cSt].
In order to which oil film equivalent is set as 10000~24000, if using using low viscosity rolling oil or slow down logical plate speed
Method well known to degree etc..
Chemical grinding is logical to be less than using the etching solution of Sulfuric-acid-hydrogen-peroxide-water system or ammonia-hydrogen peroxide-water system etc.
Normal concentration and carry out for a long time.
Also, the preferably standard deviation of the surface roughness Rz on the very thin layers of copper surface measured using contact pin type roughmeter
Difference is 0.6 μm or less.If the surface according to the very thin layers of copper surfaces measured using contact pin type roughmeter JIS B0601-1982
The standard deviation of roughness Rz is more than 0.6 μm, then has the anxiety that the unevenness for leading to the problem of etching becomes larger.Surface roughness Rz
Standard deviation be preferably 0.5 μm hereinafter, more preferably 0.4 μm hereinafter, in turn be preferably 0.3 μm hereinafter, being more preferably in turn
0.25 μm hereinafter, in turn be more preferably 0.2 μm hereinafter, in turn be more preferably 0.15 μm hereinafter, in turn be more preferably 0.1 μm with
Under.Furthermore the lower limit of standard deviation without being particularly limited to, be such as 0.001 μm or more, such as 0.005 μm or more, such as 0.01
μm or more.
Furthermore in the present invention, so-called surface roughness Rz's and its standard deviation about very thin layers of copper surface should " pole
Thin copper layer surface ", it is intended that in the surface of very thin layers of copper formation roughening treatment layer and/or refractory layer and/or antirust coat and/or chromium
When the situation of surface-treated layers such as hydrochlorate process layer and/or silane coupling process layer, the outermost surfaces of the surface-treated layer.
Furthermore on very thin layers of copper surface formed surface-treated layer when, by make appendix body copper foil and electrode away from
From being remained (with a distance from interpolar) more previously closer to uniform state, the standard deviation of above-mentioned surface roughness Rz can be reduced.
As making at a distance from electrode (interpolar distance) to remain more previously closer to the method for uniform state, can arrange
It lifts：The distance (such as 200~500mm) between cathode rotating cylinder, or diminution carrying roller is used in cathode and makes conveyance tension higher than first
Before (such as 3kgf/mm2More than) etc..
It is -40 or less that the present invention, which is by the aberration Δ L controls based on JISZ8730 on very thin layers of copper surface in one side,.
The aberration Δ L based on JISZ8730 on very thin layers of copper surface is -50 hereinafter, then for example in the very thin of the copper foil of appendix body if so
When layers of copper circuit forming surface, the contrast of very thin layers of copper and circuit is apparent from, and result visibility becomes good, can precision
The contraposition of circuit is carried out well.The aberration Δ L based on JISZ8730 on very thin layers of copper surface is preferably -45 hereinafter, more preferably
It is -50 or less.
The copper foil of the appendix body of the present invention is preferably to be by the aberration Δ a controls based on JISZ8730 on very thin layers of copper surface
20 or less.The aberration Δ a based on JISZ8730 on very thin layers of copper surface is 20 hereinafter, then for example in the copper foil of appendix body if so
Very thin layers of copper circuit forming surface when, the contrast of very thin layers of copper and circuit is apparent from, and result visibility becomes better
It is good, it can precisely carry out the contraposition of circuit.The aberration Δ a based on JISZ8730 on very thin layers of copper surface be preferably 15 with
Under, more preferably 10 hereinafter, be more preferably 8 or less in turn.
The copper foil of the appendix body of the present invention is preferably to be by the aberration Δ b controls based on JISZ8730 on very thin layers of copper surface
20 or less.The aberration Δ b based on JISZ8730 on very thin layers of copper surface is 20 hereinafter, then for example in the copper foil of appendix body if so
Very thin layers of copper circuit forming surface when, the contrast of very thin layers of copper and circuit is apparent from, and result visibility becomes better
It is good, it can precisely carry out the contraposition of circuit.The aberration Δ b based on JISZ8730 on very thin layers of copper surface be preferably 15 with
Under, more preferably 10 hereinafter, be more preferably 8 or less in turn.
It is 45 that the present invention, which is by the aberration Δ E*ab controls based on JISZ8730 on very thin layers of copper surface in another aspect,
More than.The aberration Δ E*ab based on JISZ8730 on very thin layers of copper surface is 45 or more if so, then for example in the copper of appendix body
When the very thin layers of copper circuit forming surface of foil, the contrast of very thin layers of copper and circuit is apparent from, and result visibility becomes good
It is good, it can precisely carry out the contraposition of circuit.The aberration Δ E*ab based on JISZ8730 on very thin layers of copper surface is preferably 50
More than, more preferably 55 or more, and then more preferably 60 or more.It is so-called about very thin layers of copper surface furthermore in the present invention
Aberration Δ L's, Δ a, Δ b and Δ E*ab based on JISZ8730 is somebody's turn to do " very thin layers of copper surface ", it is intended that in the table of very thin layers of copper
Face forms roughening treatment layer and/or refractory layer and/or antirust coat and/or chromating layer and/or silane coupling process layer etc.
When the situation of surface-treated layer, the outermost surfaces of the surface-treated layer.
Herein, above-mentioned aberration Δ L, Δ a, Δ b are to be utilized respectively colour difference meter to be measured, take black/white/red green/Huang/
Indigo plant, the overall target indicated using the L*a*b colour systems based on JIS Z8730, and it is expressed as Δ L：White black, Δ a：It is red
Green, Δ b：Champac.Also, Δ E*ab is indicated with following formula using these aberration.
Above-mentioned aberration can utilize control to form the plating condition of very thin layers of copper and adjust, also can be by the table of very thin layers of copper
Implement roughening treatment and adjust roughening treatment layer is arranged in face.
In the plating condition of very thin layers of copper is formed using control and when adjusting the situation of above-mentioned aberration, using electrolysis plating,
When this situation, very thin layers of copper can be made using following electrolyte composition and manufacturing condition.Above-mentioned aberration can be by improving pole
Thin copper layer formation when current density and/or reduce plating solution in copper concentration and/or improve plating solution line flow velocity and into
Row adjustment.
＜ electrolyte forms ＞
Copper：90~110g/L
Sulfuric acid：90~110g/L
Chlorine：50~100ppm
Leveling agent 1 (bis- (3- sulfopropyls) disulphide)：10~30ppm
Leveling agent 2 (amine compounds)：10~30ppm
The amine compounds of following below formula can be used in above-mentioned amine compounds.
(in above-mentioned chemical formula, R1And R2Alkyl, unsaturated hydrocarbons are replaced by hydroxy alkyl, ether, aryl, aromatic series to be selected from
Person in the group that base, alkyl are formed)
＜ manufacturing conditions ＞
Current density：70~100A/dm2
Electrolyte temperature：50~60 DEG C
Electrolyte linear velocity：3~5m/sec
Electrolysis time：0.5~10 minute
On the other hand, it is adjusted by implementing roughening treatment by the surface to very thin layers of copper roughening treatment layer is arranged above-mentioned
When the situation of aberration, which can carry out for example, by forming roughening particle by copper or copper alloy.Roughening treatment also may be used
For fine person.Roughening treatment layer also can be for by appointing in the group being made of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc
The simple substance of one or the layer etc. constituted containing wantonly a kind or more of alloy.Also, also can Yu Youtong or copper alloy formation roughening particle
Afterwards, it further carries out that offspring or the roughening treatment of particle three times is arranged by nickel, cobalt, copper, the simple substance of zinc or alloy etc..
When the situation of roughening treatment layer is arranged, above-mentioned aberration can adjust in the following way：Using containing copper be selected from
The plating solution of one or more of the group being made of nickel, cobalt, tungsten, molybdenum and phosphorus element had relatively previously improved current density (such as 38
~60A/dm2), shorten processing time (such as 0.1~1.5 second).
For example, as the roughening treatment to control above-mentioned aberration copper-cobalt-nickel alloy plating can by be electrolysed plating,
To form adhesion amount as 15~40mg/dm2Copper -100~3000 μ g/dm2Cobalt -100~1500 μ g/dm23 yuan of nickel be
The mode of alloy-layer is implemented.
It is that copper-plating bath of cobalt-nickel alloy coating and an example of plating condition are discussed further below to form such 3 yuan：
Plating bath forms：10~20g/L of Cu, 1~10g/L of Co, 1~10g/L of Ni
PH value：1~4
Temperature：30~50 DEG C
Current density Dk：38~55A/dm2
Plating time：0.3~1.5 second, more preferably 0.3~1.3 second
Also, in setting be not roughening treatment containing Ni Alloy Plating coating (such as Ni-W alloy plateds, Ni-Co-P close
Golden plating, Ni-Zn alloy plateds) situation when, above-mentioned aberration can be adjusted in the following way：By the Ni's in plating solution
Concentration is set as the 2 times or more of the concentration of other elements, and current density is set as 0.1 relatively previously low~2A/dm2, when by plating
Between be set as long to 20 seconds or more (such as 20 seconds~40 seconds).
Also, have carrier, in the appendix body of lamination middle layer on carrier and the very thin layers of copper in middle layer
Copper foil can also have one layer or more selected from by refractory layer, antirust coat, chromating layer and silane on above-mentioned roughening treatment layer
The layer that coupling process layer is formed.
Also, can have refractory layer, antirust coat on above-mentioned roughening treatment layer, can have on above-mentioned refractory layer, antirust coat
Chromating layer can also have silane coupling process layer on above-mentioned chromating layer.
Also, the copper foil of above-mentioned appendix body can 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 also can be insulating resin
Layer.
Also, the copper foil of appendix body can be also selected from having roughening treatment layer on carrier in having one layer or more on carrier
Layer in the group be made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer.It is above-mentioned
Roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer can be arranged using well known method,
Also can be arranged by the method described in this case specification, claims, attached drawing.In by carrier, oneself has at above-mentioned roughening
When managing the surface side of layer etc. laminated on the situation of the supports such as resin substrate, above-mentioned roughening is selected from one layer or more is arranged on carrier
The case where process layer, refractory layer, antirust coat, chromating layer, silane are coupled the layer in process layer has carrier and support
The advantages of being not easily stripped.
Above-mentioned resin layer can be adhesive agent, also can be the insulating resin layer of attachment semi-hardened state (B-stage state).Half
Hardening state (B-stage state) includes following state：It, can be by the insulating resin even if touching its surface with finger also to feel without adhesion
Layer overlaps and takes care of, if further being heated, can cause sclerous reaction.
Also, above-mentioned resin layer can contain thermosetting resin, also can be thermoplastic resin.Also, above-mentioned resin layer can also contain
Thermoplastic resin.Above-mentioned resin layer also can contain well known resin, hardening of resin agent, compound, hardening accelerator, dielectric substance,
React catalyst, crosslinking agent, polymer, prepreg, framework material etc..Also, institute in following document for example can be used in above-mentioned resin layer
The substance of record is (resin, hardening of resin agent, compound, hardening accelerator, dielectric substance, reaction catalyst, crosslinking agent, polymer, pre-
Leaching body, framework material etc.) and/or resin layer forming method, forming apparatus and formed, the document is International Publication number
No. WO2008/004399, International Publication number WO2008/053878, International Publication number WO2009/084533, Japanese Unexamined Patent Publication
Flat No. 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 2002-
No. 179772, Japanese Unexamined Patent Publication 2002-359444, Japanese Unexamined Patent Publication 2003-304068, Japanese Patent No. 3992225, Japan
Special open 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication 2004-82687, Japanese Patent No. 4025177
Number, Japanese Unexamined Patent Publication 2004-349654, Japanese Patent No. 4286060, Japanese Unexamined Patent Publication 2005-262506, Japanese Patent No.
No. 4570070, it is Japanese Unexamined Patent Publication 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, international public
The number of beginning the compilation of WO2004/005588, Japanese Unexamined Patent Publication 2006-257153, Japanese Unexamined Patent Publication 2007-326923, Japanese Unexamined Patent Publication 2008-
No. 111169, Japanese Patent No. 5024930, International Publication number WO2006/028207, Japanese Patent No. No. 4828427, day
This special open 2009-67029, International Publication number WO2006/134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication
No. 2009-173017, International Publication number WO2007/105635, Japanese Patent No. 5180815, International Publication number
WO2008/114858, International Publication number WO2009/008471, Japanese Unexamined Patent Publication 2011-14727, International Publication number
WO2009/001850, International Publication number WO2009/145179, International Publication number WO2011/068157, Japan Patent are special
Open No. 2013-19056.
Also, the type of above-mentioned resin layer is not particularly limited, preferably, can for example enumerate containing selected from following ingredient
The resin of one or more of group：Epoxy resin, polyimide resin, multi-functional cyanate esters, maleoyl- are sub-
Amine compounds, poly- maleimide compounds, maleimide system resin, aromatic series maleimide tree
Fat, polyvinyl acetal resin, amine ester (urethane) resin, polyether sulfone (be also known as polyethersulphone,
Polyethersulfone), polyether sulfone (being also known as polyethersulphone, polyethersulfone) resin, aromatic series
Polyamide, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamidoimide tree
Fat, rubber modified epoxy resin, phenoxy resin, carboxyl modification acrylonitrile-butadiene resin, polyphenylene oxide, double maleoyl-s
Imines cyanate resin, thermosetting polyphenylene ether resin, cyanate ester system resin, the acid anhydrides of carboxylic acid, polybasic carboxylic acid acid anhydrides, have can
Bis- (4- cyanatephenyls) propane of linear polymer, polyphenylene oxide resin, 2,2- of crosslinked functional group, phosphorous phenolate are closed
Bis- (the 4- glycidyl phenyl) propane of object, manganese naphthenate, 2,2-, polyphenylene oxide-cyanate ester based resin, siloxanes modify polyamide acyl
Imide resin, hydrocyanic ester resin, phosphine nitrile system resin, rubber modified polyamide-imide resin, isoprene, hydrogenation type polybutadiene
Alkene, polyvinyl butyral, phenoxy group, macromolecule epoxy resin, aromatic polyamide, fluororesin, bis-phenol, block copolymerized polyimide
Resin and hydrocyanic ester resin.
Also, above-mentioned epoxy resin, which is intramolecular, has 2 or more epoxy groups, as long as and to can be used for electrical, electronics material
Expect purposes, then can especially use without problems.Also, above-mentioned epoxy resin preferably has 2 or more epoxies third using intramolecular
The compound of base carries out epoxy resin made of epoxidation.Also, can be by a kind or 2 in the group being made of following ingredient
Kind or more mixing and use：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 to be aoxidized from the miscellaneous -10- phospho hetero phenanthrenes -10- of 9,10- dihydro-9-oxies
The epoxy resin that the form of the derivative of object 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, it can use
In the purposes of formation capacitor layer, and increase the capacitance of capacitor circuit.The dielectric substance (dielectric substance filler) is to use BaTiO3、
SrTiO3、Pb(Zr-Ti)O3(common name PZT), PbLaTiO3PbLaZrO (common name PLZT), SrBi2Ta2O9Tools such as (common name SBT)
There is the dielectric substance powder of the composite oxides of perovskite (Perovskite) structure.
Dielectric substance (dielectric substance filler) also can 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 grain 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
Grain size.
Resin and/or resin combination and/or compound contained in above-mentioned resin layer is set to be dissolved in such as Methylethyl
Ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetylamide, N- methylpyrrole pyridines ketone, toluene, methanol, ethyl alcohol, propylene glycol
Monomethyl ether, dimethylformamide, dimethylacetylamide, cyclohexanone, ethyl Cellosolve, N- methyl -2- Pyrrolizidines ketone, N, N- diformazans
Resin liquid (resin varnish) is made in yl acetamide, n,N-Dimethylformamide equal solvent, for example, by print roll coating method etc.
Be coated on the very thin layers of copper side surface of the copper foil of above-mentioned appendix body, be then optionally thermally dried, remove solvent and
As B-stage state.As long as dry for example using hot-air drying stove, as long as drying temperature is 100~250 DEG C, is preferably
130~200 DEG C.Usable solvent dissolves the constituent of above-mentioned resin layer, and be made resin solid content ingredient 3wt%~
The resin of 70wt%, preferably 3wt%~60wt%, preferably 10wt%~40wt%, more preferably 25wt%~40wt%
Liquid.It is most preferably molten using the progress of the mixed solvent of methyl ethyl ketone and cyclopentanone at this stage furthermore for the viewpoint of atmosphere
Solution.Furthermore solvent is preferably the solvent for the range for the use of boiling point being 50 DEG C~200 DEG C.
Also, above-mentioned resin layer is preferably resin flow when being measured according to the MIL-P-13949G in MIL standards
For the semi-hardened resin film of 5%~35% range.
In this case specification, so-called resin flow refers to making tree certainly according to the MIL-P-13949G in MIL standards
The surface treatment copper foil for the attached resin that fat thickness is 55 μm takes 4 10cm square samples, in the state for making 4 samples overlap
Under (laminate), in 171 DEG C of press temperature, pressing pressure 14kgf/cm2, be bonded under conditions of 10 minutes pressing times,
It is flowed out according to the resin measured at this time obtained by weight as a result, the value calculated based on number 1.
[number 1]
The surface treatment copper foil (surface treatment copper foil of attached resin) for having above-mentioned resin layer is used with following aspect：It will
Overall thermal crimp after overlapping and makes the resin layer thermmohardening by the resin layer and base material, then in surface treatment copper foil be appendix body
Copper foil very thin layers of copper situation when, remove carrier and expose very thin layers of copper (expose certainly be the very thin layers of copper centre
Layer side surface), form specific Wiring pattern from the surface with the roughening treatment side of surface treatment copper foil phase side on the contrary.
If using the surface treatment copper foil of the attached resin, prepreg material when manufacture multilayer printed wiring board can be reduced
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 not using preimpregnation completely
Body material can also manufacture copper-cover laminated plate.Also, at this point, insulating resin priming paint can be also coated on to the surface of base material and further
Improve the flatness on surface.
Furthermore when without using the situation of prepreg material, the material cost of prepreg material can be saved, in addition, lamination walks
Suddenly also become simple, therefore in economically advantageously, and have the following advantages：Only manufacture the thickness degree of prepreg material
The thickness of multilayer printed wiring board is thinning, and the thickness that can manufacture 1 layer is 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, there is following situation：Adhesive force reduces, and prepreg material general is deposited in not being situated between
When the surface treatment copper foil of the attached resin is on the base material 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：It is difficult in 1 application step
The resin layer of target thickness is formed, and needs extra fee of material and number of steps, so in economically becoming unfavorable.
Furthermore in the situation that the surface treatment copper foil with resin layer is used to manufacture very thin multilayer 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 multilayer board is reduced, so preferably.
In turn, by electronic component mounting class on printed circuit board, and printed circuit board is completed.In the present invention, " print
Printed circuit board " also includes printed circuit board so equipped with electronic component class and printed circuit board and printed base plate.
Also, the printed circuit 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, also can be used the printed base plate equipped with the electronic component class and make e-machine.Hereinafter, table
Show the example of the manufacturing step of the printed circuit board of the copper foil of several appendix bodies using the present invention.
One embodiment of the manufacturing method of the printed circuit board of the present invention, which contains, to have the following steps：Prepare the appendix of the present invention
The copper foil and insulating substrate of body；By the copper foil of above-mentioned appendix body and insulating substrate lamination；And so that very thin layers of copper side and insulation base
The mode of plate opposite direction is by after the copper foil of above-mentioned appendix body and insulating substrate lamination, by shelling the carrier of the copper foil of above-mentioned appendix body
From the step of and form copper-cover laminated plate, thereafter, by semi-additive process, improve in semi-additive process, part addition process and subtractive process
Any method formed circuit.Insulating substrate can also be set as internal layer circuit entrance.
In the present invention, so-called semi-additive process refers to relatively thin electroless in being carried out on insulating substrate or copper foil seed layer
Plating after forming pattern, using plating and etches the method for forming conductive pattern.
Therefore, contain following step using an embodiment of the manufacturing method of the printed circuit board of the present invention of semi-additive process
Suddenly：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body is removed；
Above-mentioned carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin
Layers of copper completely removes；
In setting through-hole and/or blind hole on the above-mentioned resin exposed by using the above-mentioned very thin layers of copper of etching removal；
Removing glue Slag treatment is carried out to the region containing above-mentioned through-hole and/or blind hole；
In containing above-mentioned resin and the region of above-mentioned through-hole and/or blind hole, electroless plating coating is set；
In setting plating resist on above-mentioned electroless plating coating；
Above-mentioned plating resist is exposed, thereafter, removal is formed with the plating resist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned plating resist；
Remove above-mentioned plating resist；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.
Contained using the another embodiment of the manufacturing method of the printed circuit board of the present invention of semi-additive process and is had the following steps：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Removing glue Slag treatment is carried out to the region containing above-mentioned through-hole and/or blind hole；
Above-mentioned carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin
Layers of copper completely removes；
In containing above-mentioned resin and above-mentioned through-hole and/or blind hole by exposing using the above-mentioned very thin layers of copper of removal such as etching
Region be arranged electroless plating coating；
In setting plating resist on above-mentioned electroless plating coating；
Above-mentioned plating resist is exposed, thereafter, removal is formed with the plating resist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned plating resist；
Remove above-mentioned plating resist；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.
Contained using the another embodiment of the manufacturing method of the printed circuit board of the present invention of semi-additive process and is had the following steps：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Above-mentioned carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin
Layers of copper completely removes；
Removing glue Slag treatment is carried out to the region containing above-mentioned through-hole and/or blind hole；
In containing the above-mentioned resin and above-mentioned through-hole that expose by 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；
In setting plating resist on above-mentioned electroless plating coating；
Above-mentioned plating resist is exposed, thereafter, removal is formed with the plating resist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned plating resist；
Remove above-mentioned plating resist；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.
Contained using the another embodiment of the manufacturing method of the printed circuit board of the present invention of semi-additive process and is had the following steps：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body is removed；
Above-mentioned carrier will be removed by using the methods of the etching of the etchant solutions such as acid or plasma and exposed very thin
Layers of copper completely removes；
In the surface of the above-mentioned resin exposed by using the above-mentioned very thin layers of copper of etching removal, electroless plating coating is set；
In setting plating resist on above-mentioned electroless plating coating；
Above-mentioned plating resist is exposed, thereafter, removal is formed with the plating resist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned plating resist；
Remove above-mentioned plating resist；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 being protected by plating resist in lamination metal foil on insulating layer
Inverter circuit forming portion removes resist, utilizes (quick) etching removal after thickening the copper thickness of circuit forming portion by being electrolysed plating
Metal foil other than foregoing circuit forming portion, thus in the method for forming circuit on insulating layer.
Therefore, using improve semi-additive process the present invention printed circuit board manufacturing method an embodiment contain as
Lower step：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Removing glue Slag treatment 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 in above-mentioned；
In the very thin layers of copper surface removed above-mentioned carrier and exposed, plating resist is set；
After above-mentioned plating resist is set, circuit is formed by being electrolysed plating；
Remove above-mentioned plating resist；And
The very thin layers of copper exposed by removing above-mentioned plating resist using fast-etching removal.
Contained using the another embodiment of the manufacturing method of the printed circuit board for the present invention for improving semi-additive process as follows
Step：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body is removed；
In setting plating resist in the very thin layers of copper that the above-mentioned carrier of stripping exposes；
Above-mentioned plating resist is exposed, thereafter, removal is formed with the plating resist in the region of circuit；
In the above-mentioned region setting electrolysis plating layer for being formed with circuit for eliminating above-mentioned plating resist；
Remove above-mentioned plating resist；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 the substrate made of conductor layer is set, optionally pass through through-hole or
Catalyst core is assigned on substrate made of via hole hole, is etched to form conductor circuit, and solder resist or plating are optionally set
After resist, in handling (optionally further carry out electrolysis plating processing) to through-hole by electroless plating on above-mentioned conductor circuit
Or via hole etc. is thickened, the method for thus manufacturing printed circuit board.
Therefore, contained using an embodiment of the manufacturing method of the printed circuit board of the present invention of part addition process as follows
Step：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Removing glue Slag treatment is carried out to the region containing above-mentioned through-hole and/or blind hole；
In above-mentioned catalyst core is assigned containing the region of through-hole and/or blind hole；
In the very thin layers of copper surface setting etching resist removed above-mentioned carrier and exposed；
Above-mentioned etching resist is exposed and forms circuit pattern；
Above-mentioned very thin layers of copper and above-mentioned catalyst are removed using the methods of etching or plasma for using the etchant solutions such as acid
Core, and form circuit；
Remove above-mentioned etching resist；
In using using the etchant solutions such as acid etching or the methods of plasma above-mentioned very thin layers of copper of removal and above-mentioned touch
Solder resist or plating resist is arranged in matchmaker's core and the above-mentioned insulating substrate surface exposed；And
In the region that above-mentioned solder resist or plating resist are not arranged, electroless plating coating is set.
In the present invention, so-called subtractive process refers to by etching the unwanted portion of the copper foil on copper-cover laminated plate etc.
The method for removing, and forming conductive pattern to component selections.
Therefore, contain following step using an embodiment of the manufacturing method of the printed circuit board of the present invention of subtractive process
Suddenly：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Removing glue Slag treatment 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 in above-mentioned；
In the surface of above-mentioned electroless plating coating setting electrolysis plating layer；
In 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 no electricity are removed using the methods of etching or plasma for using the etchant solutions such as acid
Plating layer and above-mentioned electrolysis plating layer are solved, and forms circuit；And
Remove above-mentioned etching resist.
Contained using the another embodiment of the manufacturing method of the printed circuit board of the present invention of subtractive process and is had the following steps：
Prepare the copper foil and insulating substrate of the appendix body of the present invention；
By the copper foil of above-mentioned appendix body and insulating substrate lamination；
After by the copper foil of above-mentioned appendix body and insulating substrate lamination, the carrier of the copper foil of above-mentioned appendix body 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 expose；
Removing glue Slag treatment 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 in above-mentioned；
Shade is formed in the surface of above-mentioned electroless plating coating；
In the surface for the above-mentioned electroless plating coating for not forming shade setting electrolysis plating layer；
In 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 no electricity are removed using the methods of etching or plasma for using the etchant solutions such as acid
Plating layer is solved, and forms circuit；And
Remove above-mentioned etching resist.
Also can be without setting through-hole and/or blind hole the step of and subsequent de-smear step.
Herein, the manufacturing method of the printed circuit board of the copper foil of the appendix body using the present invention is explained in detail using schema
Concrete example.Furthermore it herein, is said by taking the copper foil of the appendix body with the very thin layers of copper for being formed with roughening treatment layer as an example
Bright, but it is not limited to this, using the copper foil of the appendix body with the very thin layers of copper for not forming roughening treatment layer, also can similarly into
The manufacturing method of the following printed circuit boards of row.
First, as shown in Fig. 1-A, prepare the copper foil of the appendix body for the very thin layers of copper that there is surface to be formed with roughening treatment layer
(the 1st layer).
Secondly, as shown if figure 1-b, in being 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 Fig. 1-C, by removing resist after forming circuit coating, and the electricity of specific shape is formed
Road coating.
Secondly, as depicted in fig. 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, and the copper foil (the 2nd layer) of another appendix body is then adhered to from very thin layers of copper side.
Secondly, as shown in Fig. 2-E, carrier is removed from the copper foil of the 2nd layer of appendix body.
Secondly, as shown in Fig. 2-F, laser opening is carried out in the specific position of resin layer, circuit coating is made to expose and be formed
Blind hole.
Secondly, as shown in Fig. 3-G, it is embedded to copper in blind hole, forms through-hole filler.
Secondly, it as shown in Fig. 3-H, is plated on through-hole filler, forming circuit in a manner of the C of the B of above-mentioned Fig. 1 and Fig. 1
Layer.
Secondly, as shown in Fig. 3-I, carrier is removed from the copper foil of the 1st layer of appendix body.
Secondly, as shown in Fig. 4-J, the very thin layers of copper on two surfaces is removed by fast-etching, the circuit in resin layer is made to plate
Expose on the surface of layer.
Secondly, as shown in Fig. 4-K, in forming convex block on the circuit coating in resin layer, in forming copper post on the solder.Such as
This makes the printed circuit board of the copper foil using the appendix body for having the present invention.
The copper foil of the appendix body of the present invention can be used in (the 2nd layer) of the copper foil of above-mentioned another appendix body, and previously attached can be used
The copper foil of carrier, and then common copper foil also can be used.Also, 1 layer can be further formed on the 2nd layer of circuit shown in Fig. 3-H
Or multilayer circuit, it can be formed by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method
These circuits.
Also, the copper foil of the appendix body used in above-mentioned 1st layer can also have in the carrier side surface of the copper foil of the appendix body
Substrate.By having the substrate, the copper foil of the appendix body used in the 1st layer to be supported, become to be not likely to produce gauffer, therefore have
The advantages of productivity improves.Furthermore as long as aforesaid substrate plays the effect of the copper foil for the appendix body for supporting to be used in above-mentioned 1st layer
Whole substrates may be used in fruit.For example, carrier, prepreg, resin layer or the well known load described in this case specification can be used
Body, prepreg, resin layer, metallic plate, metal foil, the plate of inorganic compound, the foil of inorganic compound, organic compound plate,
The foil of organic compound is as aforesaid substrate.
In 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 before the step of above-mentioned very thin layers of copper side surface of the copper foil in above-mentioned appendix body forms resin layer, it is more excellent
It is selected as being formed before the step of above-mentioned very thin layers of copper side surface of the copper foil in appendix body forms circuit.
The aberration on the copper foil control pole thin copper layer surface of the appendix body of the present invention, thus it is clear with the contrast of circuit coating
Clear, visibility is good.Therefore, in the manufacturing step shown in such as Fig. 1-C of printed circuit board as described above, circuit can be made
Plating fineness is formed in specific position well.Also, according to the manufacturing method of printed circuit board as described above, become circuit
Coating is embedded to the composition of resin layer, therefore when utilizing fast-etching to remove very thin layers of copper as shown in such as Fig. 4-J, is passed through
Resin layer protects circuit coating, keeps its shape, thus becomes easy to form fine circuits.Also, due to being protected by resin layer
Circuit coating, so resistance to electron mobility is improved, the conducting of the wiring of suppression circuit well.Therefore, become easy to be formed it is micro-
Thin circuit.Also, when removing very thin layers of copper by fast-etching as shown in Fig. 4-J and Fig. 4-K, the exposed surface shape of circuit coating
It at the shape being recessed from resin layer, therefore becomes easy respectively at forming convex block on the circuit coating, and then forms copper thereon
Column, manufacture efficiency improve.
Furthermore it is embedded to resin (resin) and well known resin, prepreg can be used.Such as BT (double maleoyl-s can be used
Three mouthfuls of wells of imines) resin or it is impregnated with glass cloth, that is, prepregs of BT resins, Ajinomoto Fine-Techno limited liability companies
The ABF films or ABF of manufacture.Also, above-mentioned embedment resin can contain thermosetting resin, also can be thermoplastic resin.Also, above-mentioned embedment
Resin can also contain thermoplastic resin.The type of above-mentioned embedment resin is not particularly limited, and as preferred person, such as can be enumerated：
Including epoxy resin, polyimide resin, multi-functional cyanate esters, maleimide compounds, polyvinyl alcohol
Tree including acetate resin, amine ester resin, block copolymerization polyimide resin, block copolymerization polyimide resin etc.
Fat 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 are sub-
Amine film, liquid crystalline polymer film, fluororesin film etc..
＜ peel strengths (N/m) ＞
The copper foil of the appendix body of the present invention is that very thin layers of copper side is attached at insulation base by (1) in normal temperature and pressure state (normality)
Plate, and/or (2) pass through in air, pressure：20kgf/cm2Carry out 220 DEG C × 2 hours heating and by very thin layers of copper side heat
After crimping and being attached at insulating substrate, and/or (3) pass through in air, pressure：20kgf/cm2It carries out 220 DEG C × 2 hours
Heating and very thin layers of copper side is thermally compressed after being attached at insulating substrate, (do not apply pressure in nitrogen atmosphere, under normal pressure
State, under atmospheric pressure) carry out 2 heating in 180 DEG C × 1 hour after, utilize load measuring gauge to stretch carrier side, according to JIS C
Each peel strength when the 6471 very thin layers of copper of stripping is preferably 2~100N/m.If the peel strength does not reach 2N/m, have in printing
If the anxiety that very thin layers of copper is removed from carrier in the manufacture of circuit board has more than 100N/m and applies extra power, example when stripping
It is peeling-off in embedment resin and the interface of very thin layers of copper in such as above-mentioned implantation (embedding inlay technique (Enbedded Process))
Anxiety.The peel strength is more preferably 2~50N/m, and then more preferably 2~20N/m.
[embodiment]
Hereinafter, being illustrated based on Examples and Comparative Examples.Furthermore the present embodiment only as an example of, be not limited to this
Example.
1. the manufacture of the copper foil of appendix body
As carrier, prepare the strip electrolytic copper foil or rolled copper foil of the thickness for having described in table 1,3,4.
Electrolytic copper foil is to be manufactured under conditions of described in table 1,3,4, or use JX Nippon Mining＆Metals
The JTC foils of company's manufacture.
Rolled copper foil is to manufacture as follows.Specific casting in bronze ingot is manufactured, after carrying out hot rolling, repeats 300~800 DEG C
Continuous annealing line annealing and cold rolling, and obtain 1~2mm thickness calendering plate.It will using 300~800 DEG C of continuous annealing lines
The calendering plate anneals and is allowed to recrystallize, it is final carry out cold rolling until table 1,3,4 thickness, and obtain copper foil.In table 1,3,4
Indicate rolling condition at this time (high glaze rolls or usually rolls, oil film equivalent)." high glaze calendering " and " usually calendering " is
It is (cold after final recrystallization annealing to indicate that the value for being utilized respectively the oil film equivalent described in table 1,3,4 carries out final cold rolling
It rolls)." refined copper " of table 1,3,4 is indicated through the standardized refined coppers of JIS H3100C1100." oxygen-free copper " of table 1,3,4 is to indicate
Through the standardized oxygen-free coppers of JIS H3100C1020." ppm " of addition element described in table 1,3,4 is to indicate quality ppm.
Also, " refined copper+Ag 180ppm " on such as carrier column of table 1,3,4 is to be shown in 180 mass ppm of refined copper addition Ag.
By utilized under the following conditions roll-to-roll type continuously plate wiring to the glassy surface (shiny side) of the copper foil into
Row is electroplated and forms middle layer.
“Ni”：Nickel plating
(liquid composition) nickel sulfate：270~280g/L, nickel chloride：35~45g/L, nickel acetate：10~20g/L, boric acid：15
~25g/L, gloss agent：Saccharin, butynediols：5~15ppm, lauryl sodium sulfate：55~75ppm
(pH value) 4~6
55~65 DEG C of (liquid temperature)
(current density) 1~11A/dm2
(conduction time) 1~20 second
·“Ni-Zn”：Nickel zinc alloy plating
Under the formation condition of above-mentioned nickel plating, zinc sulfate (ZnSO is added in nickel plating solution4) form zinc, Yu Xinnong
Degree：It is adjusted in the range of 0.05~5g/L and forms nickel zinc alloy coating.
·“Cr”：Chromium plating
(liquid composition) CrO3：200~400g/L, H2SO4：1.5~4g/L
(pH value) 1~4
45~60 DEG C of (liquid temperature)
(current density) 10~40A/dm2
(conduction time) 1~20 second
" chromate "：It is electrolysed the processing of pure chromium hydrochlorate
(liquid composition) potassium bichromate：1~10g/L, zinc：0g/L
(pH value) 7~10
40~60 DEG C of (liquid temperature)
(current density) 0.1~2.6A/dm2
(coulomb amount) 0.5~90As/dm2
(conduction time) 1~30 second
" Zn- chromate "：Zinc chromate processing
Under above-mentioned electrolysis pure chromium hydrochlorate treatment conditions, zinc sulfate (ZnSO is added in liquid4) form zinc, Yu Xinnong
Degree：It is adjusted in the range of 0.05~5g/L and carries out zinc chromate processing.
·“Ni-Mo”：Nickel-molybdenum alloy plating
(liquid composition) sulfuric acid Ni hexahydrates：50g/dm3, sodium molybdate dihydrate：60g/dm3, sodium citrate：90g/dm3
30 DEG C of (liquid temperature)
(current density) 1~4A/dm2
(conduction time) 3~25 seconds
" organic "：Organic matter layer formation is handled
Pass through the aqueous solution leaching of 40 DEG C of carboxyl benzotriazole (CBTA) and liquid temperature, pH value 5 that will be containing 1~30g/L of concentration
It bathes and sprays 20~120 seconds and carry out.
·“Co-Mo”：Cobalt molybdenum alloy plating
(liquid composition) sulfuric acid Co：50g/dm3, sodium molybdate dihydrate：60g/dm3, sodium citrate：90g/dm3
30 DEG C of (liquid temperature)
(current density) 1~4A/dm2
(conduction time) 3~25 seconds
·“Ni-P”：Nickel-phosphorus alloy plating
(liquid composition) Ni：30~70g/L, P：0.2~1.2g/L
(pH value) 1.5~2.5
30~40 DEG C of (liquid temperature)
(current density) 1.0~10.0A/dm2
(conduction time) 0.5~30 second
Then, it is continuously plated on wiring in roll-to-roll type, passes through the thickness described in plating table 1,3,4 under the conditions of shown in table
Degree very thin layers of copper and be formed in middle layer, to manufacture the copper foil of appendix body.
It is surface-treated shown in table 2,5,6 under condition (surface treatment 1~3) and table is carried out to the surface of above-mentioned very thin layers of copper
Surface treatment.Herein, about surface treatment mode, the schematic diagram for being electrolysed coating step in the way of the fortune foil of rotating cylinder will be used
It is shown in Fig. 5.Also, the signal of electrolysis coating step in the way of the curved fortune foil of hair clip will be used to be illustrated in Fig. 6.Also, about
Surface treatment mode, the Examples and Comparative Examples for being recorded as " rotating cylinder " are that surface treatment 1~3 is handled by " rotating cylinder ".
Equally, the Examples and Comparative Examples for being recorded as " hair clip is curved " are that surface treatment 1~3 is handled by " hair clip is curved ".
Also, the copper foil of the appendix body of embodiment 3,5,7,10~18 be in carried out on surface-treated layer following resistance to heat treatment,
Chromic acid salt treatment, silane coupling processing.
Also, embodiment 20 only carries out resistance to heat treatment.Embodiment 22 only carries out chromic acid salt treatment.Embodiment 24 only carries out silane
Coupling is handled.Embodiment 1,26 sequentially carries out chromic acid salt treatment and silane coupling processing.
Resistance to heat treatment (forming refractory layer)
Liquid forms：5~20g/L of nickel, 1~8g/L of cobalt
PH value：2~3
Liquid temperature：40~60 DEG C
Current density：5~20A/dm2
Coulomb amount：10~20As/dm2
Chromic acid salt treatment (forms chromating layer)
Liquid forms：1~10g/L of potassium bichromate, 0~5g/L of zinc
PH value：3~4
Liquid temperature：50~60 DEG C
Current density：0~2A/dm2(in order to carry out dipping chromic acid salt treatment)
Coulomb amount：0~2As/dm2(in order to carry out dipping chromic acid salt treatment)
Silane coupling processing (forms silane and is coupled process layer)
By 60 DEG C of aqueous solutions of the spray alkoxy silane containing 0.2~2 mass % and pH value 7~8, and carry out silane
Coupling agent coating process.
Furthermore the plating bath of above-mentioned surface treatment is shown in table 7, the plating bath that very thin layers of copper is formed is shown in table 8.
2. the evaluation of the copper foil of appendix body
For each sample of Examples and Comparative Examples made as described above, various evaluations are proceeded as follows.
The measurement of surface chromatic aberration：
The colour difference meter MiniScan XE Plus manufactured using HunterLab companies, according to JISZ8730 to appendix body
The surface treated surface of the very thin layers of copper of copper foil is (in the situation for carrying out resistance to heat treatment, the coupling processing of chromic acid salt treatment, silane
When, it is after the processing finally carried out) it is measured with white aberration Δ L, Δ a, Δ b, Δ E*ab.Furthermore it is above-mentioned
Colour difference meter is that the measured value of white board is set as Δ E*ab=0, will be covered with black sack and survey when dark place is measured
Definite value is set as Δ E*ab=90, to correcting chromatic aberration.Wherein, Δ E*ab is to use L*a*b colour systems, is set as Δ L：In vain
Black, Δ a：Red green, Δ b：Champac is simultaneously measured based on following formula.Herein, aberration Δ E*ab is with zero definition white, with 90
Define black：
Furthermore the aberration Δ L based on JIS Z8730 of the tiny areas such as copper circuit surface, Δ a, Δ b, Δ E*ab are for example
The small face of electricity Se Industries, Incs of Japan manufacture can be used to be divided colour difference meter (model：VSS400 etc.) or SugaTest
The small face spectral photometric colour measuring meter (model of Instruments limited liability companies manufacture：SC-50 μ etc.) etc. well known to measurement device
It is measured.
The metal adhering amount of middle layer：
Nickel adhesion amount is the nitric acid sample dissolution using 20 mass % of concentration, the ICP emission spectrum manufactured using SII companies
Analytical equipment (model：SPS3100 it) is measured by ICP luminesceence analyses；Zinc and chromium adhesion amount are by using 100 DEG C of temperature
And the dissolving with hydrochloric acid sample of 7 mass % of concentration, the atomic absorption spectroscopy photometer (model manufactured using VARIAN companies：
AA240FS) quantitative analysis is carried out using atom light absorption method and measure；Molybdenum adhesion amount is the mixed liquor by using nitric acid and hydrochloric acid
(concentration of nitric acid：20 mass %, concentration of hydrochloric acid：12 mass %) sample dissolution, the atom extinction point manufactured using VARIAN companies
Light photometer (model：AA240FS) quantitative analysis is carried out using atom light absorption method and measure.Furthermore above-mentioned nickel, zinc, chromium, molybdenum are attached
The measurement for the amount of wearing is to proceed as follows.First, from after the copper foil of appendix body removes very thin layers of copper, very thin layers of copper is only dissolved
Middle layer side surface is nearby (when the situation that the thickness of very thin layers of copper is 1.4 μm or more, from the middle layer side surface of very thin layers of copper
0.5 μ m-thick is only dissolved, it is only molten from the middle layer side surface of very thin layers of copper when the thickness of very thin layers of copper is not up to 1.4 μm of situation
Solve the 20% of very thin copper layer thickness), measure the adhesion amount of the middle layer side surface of very thin layers of copper.Also, after removing very thin layers of copper,
Only the middle layer side surface of dissolving carrier nearby (0.5 μ m-thick is only dissolved from surface), measures the attached of the middle layer side surface of carrier
The amount of wearing.Then, by the total of the adhesion amount of the middle layer side surface of the adhesion amount of the middle layer side surface of very thin layers of copper and carrier
Value is set as the metal adhering amount of middle layer.
Furthermore it is not readily dissolved in the hydrochloric acid of the 7 mass % of nitric acid or above-mentioned concentration of 20 mass % of above-mentioned concentration in sample
Situation when, utilize the mixed liquor (concentration of nitric acid of nitric acid and hydrochloric acid：20 mass %, concentration of hydrochloric acid：12 mass %) sample dissolution
Afterwards, the adhesion amount of nickel, zinc, chromium can be measured using the above method.
Furthermore so-called " metal adhering amount " refers to sample per unit area (1dm2) the metal adhering amount (quality).
The organic matter thickness of middle layer
In by the very thin layers of copper of the copper foil of appendix body from carrier stripping after, 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, will be from very thin layers of copper
Interbed side surface is initially set as A (nm) to concentration of carbon as 3at% depth below, will be from the middle layer side surface of carrier to carbon
Concentration is initially set as B (nm) as 3at% depth below, by the thickness of total organic matter for being set as middle layer of A and B
(nm)。
Furthermore depth direction (x：Unit nm) the measuring interval of atomic concentration of metal can also be set as 0.18~0.30nm
(SiO2Conversion).In the present embodiment, with 0.28nm (SiO2Conversion) measuring space depth direction metal atomic concentration (in splashing
It was measured every 0.1 minute in the plating time).
Furthermore the above-mentioned depth profile that the concentration of carbon obtained is measured using XPS is in the very thin layers of copper for exposing
The middle layer side surface of the carrier of interbed side surface and exposing, respectively at each sample piece long side direction be directed to away from both ends 50mm with
Each 1 position in interior region, central portion 50mm × 50mm region in 1 position add up to 3 positions, that is, be directed to and expose
Very thin layers of copper middle layer side surface and exposing carrier middle layer side surface on add up to 6 positions and be made.By the dew
The position of middle layer side surface 3 of the very thin layers of copper gone out, the carrier of exposing the measurement site at 3 positions in middle layer side surface show
In Fig. 8.Then, according to each 3 of the middle layer side surface of the very thin layers of copper for exposing and the middle layer side of the carrier of exposing
Depth profile made of the region at position, calculate respectively it is above-mentioned from the middle layer side surface of very thin layers of copper to concentration of carbon initially at
Initially become 3at% depth Bs below for 3at% depth A (nm) below and from the middle layer side surface of carrier to concentration of carbon
(nm), by the thickness of the arithmetic mean of instantaneous value of A (nm) and total organic matter for being set as middle layer of the arithmetic mean of instantaneous value of B (nm)
(nm)。
Furthermore when the size of sample smaller situation, above-mentioned region and central portion within both ends to 50mm
The region of 50mm × 50mm can also overlap.
The operating condition of XPS is shown in following.
Device：XPS measurement devices (ULVAC-PHI companies, model 5600MC)
End 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+, accelerating potential 3kV, scan area 3mm × 3mm, sputtering yield 2.8nm/min (SiO2
Conversion)
Furthermore so-called XPS, it is intended that x-ray photoelectron optical spectroscopy.In the present invention, to use ULVAC-PHI companies
Premised on XPS measurement devices (model 5600MC or ULVAC-PHI companies manufacture peddle same measurement device), in can not obtain
When the situation of such measurement device, as long as the measuring interval of each element concentration of depth direction is set as 0.10~0.30nm
(SiO2Conversion), sputtering yield is set as 1.0~3.0nm/min (SiO2Conversion), then other XPS measurement devices also can be used.
The Ni adhesion amounts on very thin layers of copper surface：
By the very thin layers of copper side of the copper foil of appendix body be attached at BT resins (the double maleimide system resins of three mouthfuls of wells,
Gas chemistry limited liability company of Mitsubishi manufactures) and carry out heating crimping in 2 hours in 220 DEG C.Thereafter, according to JIS C 6471
(method A) removes very thin layers of copper from foil carriers.Then, it by using the nitric acid sample dissolution of 20 mass % of concentration, uses
The ICP emission spectrographic analysis device (models of SII companies manufacture：SPS3100 ICP luminesceence analyses) are carried out and measure very thin layers of copper
The Ni adhesion amounts of middle layer side surface.Furthermore in pair with the middle layer side surface of very thin layers of copper mutually on the contrary the surface of side contains
When having the situation of the surface treatment of Ni, (in the thickness of very thin layers of copper near the middle layer side surface by only dissolving very thin layers of copper
For 1.4 μm or more of situation when, only dissolve 0.5 μ m-thick from the middle layer side surface of very thin layers of copper, in very thin layers of copper thickness not
When up to 1.4 μm of situation, the 20% of very thin copper layer thickness is only dissolved from the middle layer side surface of very thin layers of copper), it can measure very thin
The Ni adhesion amounts of the middle layer side surface of layers of copper.
Etching：
By the copper foil of made appendix body and base material, (Mitsubishi's gas chemistry manufactures：GHPL-832NX-A, 0.05mm × 4
Piece) lamination and after 220 DEG C carry out heating crimping in 2 hours, foil carriers are removed, very thin layers of copper is made to expose and size 250 is made
×250mm2Sample.Adjustment can utilize sulfuric acid-aqueous peroxygen solutions (SE07 of Mitsubishi's gas chemistry manufacture) to very thin layers of copper
The amount for carrying out each thickness etching passes through small-sized etching machine (the small-sized half-etching device No.K- of Ninomiya System manufactures
07003) implement whole face etching.Then, using until resin in whole face expose until needed for etching number, to the copper of appendix body
The etching of foil is evaluated.Etching condition at this time is shown in following.
(etching condition)
As etching solution, sulfuric acid-aqueous peroxygen solutions are used：The manufacture of Mitsubishi gas chemistry SE-07 20vol% (with
Stoste is diluted 5 times by water, copper concentration 18g/L).
It it is 35 ± 2 DEG C by the temperature management of etching solution.
Atomisation pressure：0.1MPa (spraying is carried out in such a way that the layers of copper to etch target vertically sprays etching solution)
Etching speed (amount for being equivalent to etching)：0.3 μm/secondary (every 1 passage of etching machine is 30 seconds)
Using above-mentioned sulfuric acid-aqueous peroxygen solutions：The SE-07 of Mitsubishi's gas chemistry manufacture carries out each thickness to very thin layers of copper
The amount of degree etching is will to utilize the gravimetric detemination JX Nippon Mining ＆Metals of electrolytic copper foil JTC when etching in advance
Etch quantity (decrement of copper layer thickness) obtained by the whole face of the electrolytic copper foil JTC (35 μm of thickness) of company's manufacture, at this time
The relationship of etching period is made chart as shown in Figure 7 and finds out, and according to the etching actually expended in Examples and Comparative Examples
Time calculates etch quantity (decrement of copper layer thickness) and finds out.
The assay method of etch quantity (decrement of copper layer thickness) is found out using following formula.
Etch quantity (decrement of copper layer thickness) (μm)=(weight (g) before etching)-(weight (g) after etching)/
(etching area (μm2(g/ μm of the density of) × copper3))
It is set as density=8.96g/cm of copper3=8.96 × 10-12g/μm3。
Specifically, obtaining thickness B=etching periods (the second) × factor alpha for being equivalent to the very thin layers of copper using etching removal
The relationship of (=0.0336) finds out the thickness B for being equivalent to the very thin layers of copper using etching removal thus according to etching period.That is,
Such as so-called B=5 μm of thickness for being equivalent to the very thin layers of copper using etching removal, it is intended that carry out 5 μm of ÷ factor alphas (=0.0336)
The case where etching in=148.8 seconds.
In this way, being measured to average, etching number maximum value-minimum value of etching number, the etching number.It will
The determinating reference of etching number relative to very thin copper layer thickness and the uneven determinating reference shown in table 10 of etching number.
The evaluation of visibility：
After being coated with plating resist in the very thin layers of copper of the copper foil of the appendix body of Examples and Comparative Examples, electrolysis plating is carried out
It applies, forms the copper plating portion of 20 μ m, 20 μm of square.Thereafter, it attempts to detect using CCD camera after removing plating resist above-mentioned
Copper plating portion.The situation for detecting 10 times in 10 times is set as " ◎ ◎ ", will detect that 9 times or more situations are set as in 10 times
" ◎ ", "○" is set as by the situation for detecting 7~8 times, and the situation for detecting 6 times is set as " △ ", will can detect 5 times or less
The case where be set as "×".
The evaluation of surface roughness：
(1) the surface roughness Rz (10 mean roughness) on very thin layers of copper surface
The contact roughmeter that limited liability company of little Ban research institutes manufactures is used according to JIS B0601-1982
SurfcorderSE-3C contact pin type roughmeters, measuring the surface roughness Rz (contact pilotage) on very thin layers of copper surface, (10 points average thick
Rugosity).The average value of the Rz (contact pilotage), is set as the value of Rz (contact pilotage) by the Rz (contact pilotage) for arbitrarily measuring 10 positions.Also, being directed to
Rz (contact pilotage) calculates the standard deviation of the value at 10 positions.
(2) middle layer forms the surface roughness of the carrier of side surface
The contact roughmeter that limited liability company of little Ban research institutes manufactures is used according to JIS B0601-1982
Surfcorder SE-3C contact pin type roughmeters measure the rough surface on the directions TD for the carrier that middle layer forms side surface
Spend Rz (contact pilotage).The average value of the Rz (contact pilotage), is set as the value of Rz (contact pilotage) by the Rz (contact pilotage) for arbitrarily measuring 10 positions.
The adhesion of very thin layers of copper and embedment resin：
In being coated with resist on the roughening treatment layer of the very thin layers of copper of the copper foil of appendix body, it is exposed, develops and will resist
Erosion agent is etched into threadiness.Secondly, by removing resist after forming circuit Cu coating, and line circuit coating is formed.Its
Secondary, in setting embedment resin in very thin layers of copper, (the BT resins of Mitsubishi's gas chemistry manufacture are (double suitable in a manner of burying circuit coating
Three mouthfuls of well resins of butylmaleimide)) and laminated resin layer.Then, it attempts in the interface peel carrier with very thin layers of copper, to this
When the number in resin layer and the interface peel of very thin layers of copper measure.It will be in the interface peel of resin layer and very thin layers of copper
Number be set as " ◎ ◎ " in 10 times for 0 situation, will be that 1 situation is set as " ◎ " in 10 times, will be 2~3 in 10 times
Secondary situation is set as "○", and the situation for 4~5 times in 10 times is set as " △ ", the situation for 6 times or more in 10 times is set as
“×”。
Middle layer forms the glossiness (%) in the directions TD of the carrier of side surface
The Grossmeters Handy Gloss of electricity Se Industries, Incs of Japan manufacture are used according to JIS Z8741
Meter PG-1, for rolled copper foil with rectangular with rolling direction (direction of travel of copper foil when calendering, width direction)
60 degree of the incidence angle in direction (TD) measure glossiness (%).Also, for electrolytic copper foil with electrolysis handle when copper foil haulage
The glossiness (%) of 60 degree of measurement frosted faces of incidence angle in the rectangular direction in direction (i.e. width direction) (TD).
Peel strength (N/m)
In air, pressure：20kgf/cm2, 220 DEG C × under conditions of 2 hours by the very thin layers of copper of the copper foil of appendix body
Side is thermally compressed and is attached at BT resins (the double maleimide system resins of three mouthfuls of wells, gas chemistry limited liability company of Mitsubishi
Manufacture).Then, carrier side is stretched using cupping machine, it is strong to measure stripping when removing very thin layers of copper according to JIS C 6471
Degree.(indicating the value in column " after 220 DEG C of baking 2h (N/m) " of table 9)
Also, after heating in above-mentioned 220 DEG C × 2 hours, and then do not apply pressure (under normal pressure i.e. in nitrogen atmosphere
Under atmospheric pressure) and 2 heating in 180 DEG C × 1 hour are carried out, in addition to this, in the stripping for measuring each sample under the same conditions
Intensity.(indicating the value in " behind 180 DEG C of baking 1h × 2 time (N/m) " column of table 9)
In turn, before the above-mentioned heating crimping to resin each sample of (normal temperature and pressure state, that is, normality) also in from very thin layers of copper side
After attaching adhesive tape to resin substrate, carrier side is stretched using cupping machine, is measured according to JIS C 6471 and removes very thin copper
Peel strength when layer.(indicating the value in column " normality (N/m) " of table 9)
[table 8]
[table 9]
(evaluation result)
Examples 1 to 36 be very thin layers of copper surface aberration Δ L be -40 hereinafter, very thin layers of copper surface aberration Δ E*
Ab is 45 or more, and at least visibility is good.
Comparative example 1~9 is that the aberration Δ L on very thin layers of copper surface is more than -40, the aberration Δ E*ab on very thin layers of copper surface
Not up to 45, at least visibility is bad.
Claims (33)
1. a kind of copper foil of appendix body sequentially has carrier, middle layer and very thin layers of copper, and
The aberration Δ E*ab based on JISZ8730 on the very thin layers of copper surface is 45 or more.
2. the copper foil of appendix body according to claim 1, wherein the aberration based on JISZ8730 on the very thin layers of copper surface
Δ a is 20 or less.
3. the copper foil of appendix body according to claim 1, wherein the aberration based on JISZ8730 on the very thin layers of copper surface
Δ b is 20 or less.
4. the copper foil of appendix body according to claim 1, wherein the middle layer contains Ni,
By the copper foil of the appendix body after 220 DEG C are heated 2 hours, when the very thin layers of copper being removed according to JIS C 6471, the pole
The Ni adhesion amounts of the middle layer side surface of thin copper layer are 5 μ g/dm2The above 300 μ g/dm2Below.
5. the copper foil of appendix body according to claim 2 or 3, wherein the middle layer contains Ni,
By the copper foil of the appendix body after 220 DEG C are heated 2 hours, when the very thin layers of copper being removed according to JIS C 6471, the pole
The Ni adhesion amounts of the middle layer side surface of thin copper layer are 5 μ g/dm2The above 300 μ g/dm2Below.
6. the copper foil of appendix body according to claim 1, wherein use contact pin type roughness according to JIS B0601-1982
The surface roughness Rz on the very thin layers of copper surface measured is 0.2 μm or more 1.5 μm or less.
7. the copper foil of appendix body according to any one of claim 2 to 4, wherein used according to JIS B0601-1982
The surface roughness Rz on the very thin layers of copper surface that contact pin type roughmeter measures is 0.2 μm or more 1.5 μm or less.
8. the copper foil of appendix body according to claim 1, wherein use contact pin type roughness according to JIS B0601-1982
The standard deviation of the surface roughness Rz on the very thin layers of copper surface measured is 0.6 μm or less.
9. the copper foil of the appendix body according to claim 2 to 4, any one of 6, wherein make according to JIS B0601-1982
The standard deviation of the surface roughness Rz on the very thin layers of copper surface measured with contact pin type roughmeter is 0.6 μm or less.
10. the copper foil of appendix body according to claim 1, wherein it is attached under normal temperature and pressure insulating substrate to be attached at this
Behind the very thin layers of copper side surface of the copper foil of carrier, and/or
By in air, in 20kgf/cm2Pressure under carry out heating in 220 DEG C × 2 hours and be connected to insulating substrate hot pressing
Behind the very thin layers of copper side surface of the copper foil of the appendix body, and/or
By in air, in 20kgf/cm2Pressure under carry out heating in 220 DEG C × 2 hours and be connected to insulating substrate hot pressing
Behind the very thin layers of copper side surface of the copper foil of the appendix body, carried out in nitrogen atmosphere, under normal pressure 2 times 180 DEG C × 1 hour plus
After heat, in the state of through thermo-compression bonding,
Peel strength when removing the very thin layers of copper according to JIS C 6471 is 2~100N/m.
11. the copper foil of the appendix body according to claim 2 to 4,6, any one of 8, wherein will insulation under normal temperature and pressure
After substrate is attached at the very thin layers of copper side surface of the copper foil of the appendix body, and/or
By in air, in 20kgf/cm2Pressure under carry out heating in 220 DEG C × 2 hours and be connected to insulating substrate hot pressing
Behind the very thin layers of copper side surface of the copper foil of the appendix body, and/or
By in air, in 20kgf/cm2Pressure under carry out heating in 220 DEG C × 2 hours and be connected to insulating substrate hot pressing
Behind the very thin layers of copper side surface of the copper foil of the appendix body, carried out in nitrogen atmosphere, under normal pressure 2 times 180 DEG C × 1 hour plus
After heat, in the state of through thermo-compression bonding,
Peel strength when removing the very thin layers of copper according to JIS C 6471 is 2~100N/m.
12. the copper foil of appendix body according to claim 1 sequentially has the middle layer in two faces of the carrier and is somebody's turn to do
Very thin layers of copper.
13. the copper foil of the appendix body according to claim 2 to 4,6,8, any one of 10, in two faces of the carrier according to
Sequence has the middle layer and the very thin layers of copper.
14. the copper foil of appendix body according to claim 1, at least one surface of the very thin layers of copper and the carrier or
Two surfaces have roughening treatment layer.
15. the copper foil of the appendix body according to claim 2 to 4,6,8,10, any one of 12, in the very thin layers of copper and
At least one surface of the carrier or two surfaces have roughening treatment layer.
16. the copper foil of appendix body according to claim 15 has in the surface of the roughening treatment layer selected from by heat-resisting
The layer of one or more of the group that layer, antirust coat, chromating layer and silane coupling process layer are formed.
17. the copper foil of the appendix body according to claim 2 to 4,6,8,10,12, any one of 14, in the very thin layers of copper
And the carrier at least one surface or two surfaces have selected from even by refractory layer, antirust coat, chromating layer and silane
Close the layer of one or more of group that process layer is formed.
18. the copper foil of appendix body according to claim 13 has in a surface of the very thin layers of copper or two surfaces
By 1 in the group being made of roughening treatment layer, refractory layer, antirust coat, chromating layer and silane coupling process layer
Kind or more layer.
19. the copper foil of appendix body according to claim 1, in having resin layer in the very thin layers of copper.
20. the copper foil of the appendix body according to claim 2 to 4,6,8,10,12, any one of 14, in the very thin layers of copper
On have resin layer.
21. the copper foil of appendix body according to claim 14, in having resin layer on the roughening treatment layer.
22. the copper foil of appendix body according to claim 15, in having resin layer on the roughening treatment layer.
23. the copper foil of appendix body according to claim 17 is selected from this by refractory layer, antirust coat, chromic acid salt treatment
Has resin layer on the layer of one or more of the group that layer and silane coupling process layer are formed.
24. the copper foil of appendix body according to claim 18 is selected from this by refractory layer, antirust coat, chromic acid salt treatment
Has resin layer on the layer of one or more of the group that layer and silane coupling process layer are formed.
25. a kind of copper-cover laminated plate is made using the copper foil of the appendix body according to any one of claim 1 to 24
It makes.
26. a kind of printed circuit board is made using the copper foil of the appendix body according to any one of claim 1 to 24
It makes.
27. a kind of e-machine is manufactured using printed circuit board according to claim 26.
28. a kind of manufacturing method of printed circuit board contains and has the following steps：
The step of preparing the copper foil and insulating substrate of the appendix body according to any one of claim 1 to 24；
The step of by the copper foil of the appendix body and insulating substrate lamination；And
After by the copper foil of the appendix body and insulating substrate lamination, by the step for removing the foil carriers of the copper foil of the appendix body
Suddenly copper-cover laminated plate is formed,
Thereafter, circuit is formed by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method
Step.
29. a kind of manufacturing method of printed circuit board contains and has the following steps：
Circuit is formed in the very thin layers of copper side surface of the copper foil of the appendix body according to any one of claim 1 to 24
Step；
In a manner of burying the circuit in the very thin layers of copper side surface of the copper foil of the appendix body forms resin layer the step of；
In the step of forming circuit on the resin layer；
After forming circuit on the resin layer, the step of removing the carrier；And
By removing the very thin layers of copper after removing the carrier, and make to be formed in the very thin layers of copper side surface is buried in the resin
The step of circuit of layer exposes.
30. the manufacturing method of printed circuit board according to claim 29, wherein in the step for forming circuit on the resin layer
Suddenly it is to fit in the copper foil of another appendix body on the resin layer from very thin layers of copper side, uses the appendix body for fitting in the resin layer
Copper foil and the step of form the circuit.
31. the manufacturing method of printed circuit board according to claim 30, wherein fit in another attached on the resin layer
The copper foil of carrier is the copper foil of the appendix body according to any one of claim 1 to 24.
32. the manufacturing method of the printed circuit board according to any one of claim 29 to 31, wherein on the resin layer
The step of forming circuit is by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method
It carries out.
33. the manufacturing method of the printed circuit board according to any one of claim 29 to 31, and then containing in stripping
Before carrier, in the step of carrier side surface of the copper foil of appendix body forms substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-124398 | 2013-06-13 | ||
| JP2013124398 | 2013-06-13 | ||
| CN201480011096.XA CN105189829B (en) | 2013-06-13 | 2014-06-13 | The copper foil of appendix body, copper-cover laminated plate, printed circuit board (PCB), the manufacturing method of e-machine and printed circuit board (PCB) |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480011096.XA Division CN105189829B (en) | 2013-06-13 | 2014-06-13 | The copper foil of appendix body, copper-cover laminated plate, printed circuit board (PCB), the manufacturing method of e-machine and printed circuit board (PCB) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108277513A true CN108277513A (en) | 2018-07-13 |
Family
ID=52022391
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810174503.9A Pending CN108277513A (en) | 2013-06-13 | 2014-06-13 | The copper foil of appendix body, the manufacturing method of copper-cover laminated plate, printed circuit board, e-machine and printed circuit board |
| CN201480011096.XA Active CN105189829B (en) | 2013-06-13 | 2014-06-13 | The copper foil of appendix body, copper-cover laminated plate, printed circuit board (PCB), the manufacturing method of e-machine and printed circuit board (PCB) |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480011096.XA Active CN105189829B (en) | 2013-06-13 | 2014-06-13 | The copper foil of appendix body, copper-cover laminated plate, printed circuit board (PCB), the manufacturing method of e-machine and printed circuit board (PCB) |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5651811B1 (en) |
| KR (1) | KR101762049B1 (en) |
| CN (2) | CN108277513A (en) |
| TW (1) | TWI527687B (en) |
| WO (1) | WO2014200106A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101954051B1 (en) * | 2012-11-20 | 2019-03-05 | 제이엑스금속주식회사 | Copper foil with carrier |
| TWI569954B (en) * | 2013-08-29 | 2017-02-11 | Jx Nippon Mining & Metals Corp | A method of manufacturing a metal sheet, a metal foil, a connector, a terminal, a laminated body, a shielded material, a printed wiring board, a metal processing member, an electronic machine, and a printed wiring board |
| JP6522974B2 (en) * | 2015-02-07 | 2019-05-29 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, method of producing laminate, and method of producing printed wiring board |
| WO2016143117A1 (en) * | 2015-03-12 | 2016-09-15 | 三井金属鉱業株式会社 | Metal foil with carrier, and manufacturing method for wiring board |
| JP6236119B2 (en) * | 2015-06-24 | 2017-11-22 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, laminate production method, printed wiring board production method, and electronic device production method |
| KR20180113996A (en) * | 2016-02-18 | 2018-10-17 | 미쓰이금속광업주식회사 | Copper foil for manufacturing a printed wiring board, copper foil having a carrier, and copper clad laminate, and a manufacturing method of a printed wiring board using the same |
| WO2017149811A1 (en) | 2016-02-29 | 2017-09-08 | 三井金属鉱業株式会社 | Copper foil with carrier, production method for coreless support with wiring layer, and production method for printed circuit board |
| JP6471140B2 (en) * | 2016-11-30 | 2019-02-13 | 福田金属箔粉工業株式会社 | Composite metal foil, copper-clad laminate using the composite metal foil, and method for producing the copper-clad laminate |
| WO2020195748A1 (en) * | 2019-03-27 | 2020-10-01 | 三井金属鉱業株式会社 | Metal foil for printed wiring board, metal foil with carrier, and metal-clad laminate, and method for manufacturing printed wiring board using same |
| CN110996536B (en) * | 2019-12-25 | 2023-06-02 | 广东生益科技股份有限公司 | Carrier copper foil and preparation method and application thereof |
| LU101698B1 (en) * | 2020-03-18 | 2021-09-20 | Circuit Foil Luxembourg | Surface-treated copper foil for high-frequency circuit and method for producing same |
| KR102232514B1 (en) * | 2020-07-13 | 2021-03-25 | 동우 화인켐 주식회사 | Flexible window stack structure and display device including the same |
| CN114828447A (en) * | 2021-01-28 | 2022-07-29 | 鹏鼎控股(深圳)股份有限公司 | Circuit board and manufacturing method thereof |
| CN112941478A (en) * | 2021-01-29 | 2021-06-11 | 山东金宝电子股份有限公司 | Ultra-thin copper foil taking micro-arc oxidation treatment aluminum foil as carrier and preparation method thereof |
| CN113416986B (en) * | 2021-07-08 | 2022-10-11 | 江西柔顺科技有限公司 | Method for producing electrolytic copper foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031913A1 (en) * | 2011-08-31 | 2013-03-07 | Jx日鉱日石金属株式会社 | Copper foil with carrier |
| WO2013065727A1 (en) * | 2011-11-02 | 2013-05-10 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4087369B2 (en) * | 2003-11-11 | 2008-05-21 | 古河サーキットフォイル株式会社 | Ultra-thin copper foil with carrier and printed wiring board |
| JP4354955B2 (en) * | 2004-02-17 | 2009-10-28 | 日鉱金属株式会社 | Copper foil with blackened surface or layer |
| JP5156873B1 (en) * | 2012-07-25 | 2013-03-06 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
| JP5481553B1 (en) * | 2012-11-30 | 2014-04-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil with carrier |
-
2014
- 2014-06-13 JP JP2014536053A patent/JP5651811B1/en active Active
- 2014-06-13 TW TW103120685A patent/TWI527687B/en active
- 2014-06-13 KR KR1020157017525A patent/KR101762049B1/en active IP Right Grant
- 2014-06-13 CN CN201810174503.9A patent/CN108277513A/en active Pending
- 2014-06-13 CN CN201480011096.XA patent/CN105189829B/en active Active
- 2014-06-13 WO PCT/JP2014/065810 patent/WO2014200106A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031913A1 (en) * | 2011-08-31 | 2013-03-07 | Jx日鉱日石金属株式会社 | Copper foil with carrier |
| WO2013065727A1 (en) * | 2011-11-02 | 2013-05-10 | Jx日鉱日石金属株式会社 | Copper foil for printed circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5651811B1 (en) | 2015-01-14 |
| CN105189829B (en) | 2018-06-01 |
| KR20150085105A (en) | 2015-07-22 |
| TWI527687B (en) | 2016-04-01 |
| JPWO2014200106A1 (en) | 2017-02-23 |
| KR101762049B1 (en) | 2017-07-26 |
| WO2014200106A1 (en) | 2014-12-18 |
| TW201511937A (en) | 2015-04-01 |
| CN105189829A (en) | 2015-12-23 |
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