CN109072472A - Surface treatment copper foil, the manufacturing method with carrier copper foil and their copper-clad laminated board of use and printed circuit board - Google Patents
Surface treatment copper foil, the manufacturing method with carrier copper foil and their copper-clad laminated board of use and printed circuit board Download PDFInfo
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- CN109072472A CN109072472A CN201780023464.6A CN201780023464A CN109072472A CN 109072472 A CN109072472 A CN 109072472A CN 201780023464 A CN201780023464 A CN 201780023464A CN 109072472 A CN109072472 A CN 109072472A
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- copper foil
- surface treatment
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- treatment copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- 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
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Automation & Control Theory (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
There is provided when for SAP method can will be not only plating circuit adaptation and also etching to electroless copper and dry film resolution ratio also excellent surface profile assigns the surface treatment copper foil of laminated body.The surface treatment copper foil has processing surface at least side.Processing surface is 55mm according to the arithmetic average curvature Spc of the peak maximum measured ISO25178‑1More than, resin film hot pressing is connected to processing surface to handle the transferring surface shape on surface to the surface of resin film, and when by etching removal surface treatment copper foil, the arithmetic average curvature Spc for the peak maximum that the foundation ISO25178 on the surface of remaining resin film is measured is 55mm‑1More than.
Description
Technical field
The present invention relates to surface treatment copper foil, with carrier copper foil and the copper-clad laminated board and printed circuit that use them
The manufacturing method of plate.
Background technique
In recent years, the manufacturing process as the printed circuit board for the miniaturization for being suitable for circuit, is widely used semi-additive process
(SAP method).SAP method is the method for being extremely suitable for forming fine circuit, as one example, at band carrier roughening
Copper foil is managed to carry out.For example, using prepreg 12 and prime coat 13, will be provided with the very thin of roughened surface as shown in Fig. 1 and 2
Copper foil 10 crimps and is sealed at it on insulating resin substrate 11, and the insulating resin substrate 11 is to have on base substrate 11a
The insulating resin substrate (process (a)) of standby lower circuit 11b；After removing carrier (not shown), as desired by laser beam perforation
It is formed via hole 14 (process (b)).Then, ultrathin copper foil is removed by etching, to make to impart roughened surface profile
Prime coat 13 exposes (process (c)).After being applied with electroless copper 15 (process (d)) to the roughened surface, by using dry
The exposure and imaging of film 16 is sheltered (process (e)) with defined pattern, is applied electro-coppering 17 (process (f)).By dry film 16
Remove and after forming wiring portion 17a (process (g)), will be unwanted between adjacent wiring portion 17a, 17a by etching
Electroless copper 15 removes (process (h)), to obtain the wiring 18 formed with defined pattern.
For having used the SAP method of roughening treatment copper foil in this way, roughening treatment copper foil leads to from after laser beam perforation
Overetch and be removed (process (c)).Moreover, because the concaveconvex shape in the roughening treatment face of roughening treatment copper foil is transferred
To the laminated body surface for eliminating roughening treatment copper foil, therefore in process behind, it can be ensured that insulating layer (such as priming paint
Layer 13 or there is no be prepreg 12 in the case where it) adaptation with plating circuit (such as wiring 18).It should be noted that
Also it is widely used without the simulation semi-additive process (MSAP method) with the comparable copper foil removing step of process (c), but due to necessary
This 2 layers of copper foil layer and chemical plating copper layer are removed by etching in the etching work procedure (being equivalent to process (h)) after dry film removal,
Therefore compared with only etching removes 1 layer of chemical plating copper layer of SAP method, it is necessary to deeper be etched.Accordingly, it is considered to more
Etch quantity and needing reduces circuit interval, it can be said that MSAP method is poorer than SAP method in terms of fine circuits formative
It is some.That is, for the purpose that finer circuit is formed, SAP method is more advantageous.
On the other hand, it is known to control the band carrier roughening treatment copper foil of roughening grain shape.For example, patent is literary
It offers in 1 (Japanese Unexamined Patent Publication 2013-199082 bulletin) and discloses a kind of band carrier copper foil, which is characterized in that in very thin layers of copper table
Face have particle length 10% position particle root average diameter D1 be 0.2 μm~1.0 μm and particle length L1 with
The ratio L1/D1 of the average diameter D1 of grain root is 15 roughening treatment layers below.In the patent document 1, it is preferred that in pole
Thin copper layer surface, the ratio of the average diameter D1 of the average diameter D2 and particle root in the particle center of 50% position of particle length
D2/D1 is 1~4, and the ratio D2/D3 of the particle front end D3 of 90% position of the average diameter D2 and particle length in particle center
It is 0.8~1.0.In addition, the length for disclosing roughening particle in the embodiment of patent document 1 is 2.68 μm or more.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-199082 bulletin
Summary of the invention
As previously mentioned, for the SAP method for having used roughening treatment copper foil, roughening treatment copper foil is from laser beam perforation
(process (c)) is removed by etching afterwards.Moreover, the concaveconvex shape in the roughening treatment face of roughening treatment copper foil is transferred
Result to the laminated body surface for eliminating roughening treatment copper foil is to bring replica concaveconvex shape.It operates in this way,
Thereafter it can ensure insulating layer (such as prime coat 13 or there is no be prepreg 12 in the case where it) and plating electricity in process
The adaptation on road (such as wiring 18).But in order to cope with the further miniaturization of circuit, it is expected that adaptation further mentions
It is high.For this purpose, by making the concaveconvex shape in roughening treatment face have the shape of the intermediate substantially bulbous protrusion to attenuate, thus sharp
The recess portion to be attenuated with corresponding replica concaveconvex shape to centre falls into brought anchoring effect and thinks that adaptation can be achieved
Raising.But in this case, the recess portion of replica concaveconvex shape is buried by copper coating sometimes in the electroless copper of process (d)
Not or the intermediate taper portion of replica concaveconvex shape is closed and planarized by copper coating.Such replica concaveconvex shape buries
Or planarization will lead to the reduction of dry film resolution ratio and etching.That is, dry film falls into reduction to replica concaveconvex shape, as a result with
The adaptation of dry film reduces, and dry film resolution ratio reduces.In addition, in order to eliminate intermediate the becoming of electroless copper landfill replica concaveconvex shape
Remaining copper is eliminated in the part of thin recess portion, needs more to etch.
The inventors of the present invention this time obtain following opinion: being assigned by the processing surface to surface treatment copper foil by foundation
The distinctive surface profile that the arithmetic average curvature Spc for the peak maximum that ISO25178 is measured is limited is capable of providing for SAP
When method stacking can be assigned by not only plating circuit excellent adhesion but also to the etching of electroless copper also excellent surface profile
The surface treatment copper foil of body.In addition, also obtaining following opinion: by using above-mentioned surface treatment copper foil, thus in SAP method
In dry film developing procedure, extremely fine dry film resolution ratio can be realized.
Therefore, the object of the present invention is to provide one kind when being used for SAP method can will be not only plating circuit adaptation and
And also excellent surface profile assigns the surface treatment copper foil of laminated body for etching to electroless copper and dry film resolution ratio.Separately
Outside, another object of the present invention is to provide the band carrier copper foils for having such surface treatment copper foil.
According to embodiment of the present invention, a kind of surface treatment copper foil is provided, there is processing table at least side
Face,
Aforementioned processing surface is 55mm according to the arithmetic average curvature Spc of the peak maximum measured ISO25178-1More than,
By resin film hot pressing be connected to aforementioned processing surface to by the transferring surface shape on aforementioned processing surface to aforementioned
The surface of resin film, and by etching by aforementioned surfaces handle copper foil removal when, the aforementioned table of remaining aforementioned resin film
The arithmetic average curvature Spc for the peak maximum that the foundation ISO25178 in face is measured is 55mm-1More than.
Another embodiment according to the present invention provides a kind of band carrier copper foil, has: carrier；It is set to the carrier
On peeling layer；And copper foil is handled using the aforementioned surfaces that aforementioned processing surface is arranged on the outside of on the peeling layer.
Another embodiment according to the present invention, provides a kind of manufacturing method of copper-clad laminated board, which is characterized in that uses
Aforementioned surfaces handle copper foil or aforementioned strip carrier copper foil manufactures copper-clad laminated board.
Another embodiment according to the present invention, provides a kind of manufacturing method of printed circuit board, which is characterized in that uses
Aforementioned surfaces handle copper foil or aforementioned strip carrier copper foil manufactures printed circuit board.
Detailed description of the invention
Fig. 1 is the process flow chart for illustrating SAP method, for the figure for showing first half process (process (a)~(d)).
Fig. 2 is the process flow chart for illustrating SAP method, for the figure for showing later half process (process (e)~(h)).
Fig. 3 is for illustrating the figure according to the ISO25178 load curve determined and load area rate.
Fig. 4 is the load area rate Smr1 of the separation prominent peak potion and central part for illustrating to determine according to ISO25178
Figure.
Specific embodiment
Definition
The definition of the term or parameter described below used to limit the present invention.
In this specification, " the arithmetic average curvature Spc of peak maximum " is being measured according to ISO25178, expression surface
The parameter of the arithmetic mean of instantaneous value of the principal curvatures of peak maximum.The small point for indicating to contact with other objects of the value is mellow and full.On the other hand, should
Value indicates that greatly the point contacted with other objects is sharp.In brief, the arithmetic average curvature Spc of peak maximum can be described as using laser
The parameter of the measurable circularity for indicating convex portion of microscope.The arithmetic average curvature Spc of peak maximum can be by utilizing city
(such as 100 μm of defined measurement area to processing surface of the laser microscope sold22 dimensional region) surface profile carry out
Measurement is to calculate.Spc is defined by mathematical expression below.
In this specification, " load curve in face " (hreinafter referred to as " load curve ") is indicated according to ISO25178 institute
Measure, load area rate becomes the curve of 100% height from 0%.As shown in figure 3, load area rate is to indicate a certain height
Spend the parameter of the area in the region of c or more.The Smr (c) in Fig. 3 is equivalent in the load area rate of height c.As shown in figure 4, right
In by load area rate be 0% along load curve with the secant for the load curve that the difference of load area rate is 40% and draws,
It moves the secant since load area rate 0%, tangent slope is become into most gentle position and is known as in load curve
Entreat part.It will be known as straight line of equal value relative to the center portion, the smallest straight line of the quadratic sum of the deviation of y direction.It will be of equal value
Partially it is known as central part contained in the range of 0%~100% height of load area rate of straight line.By the part higher than central part
The part lower than central part is known as prominent valley by referred to as prominent peak potion.Central part indicate in the early stage wear away after with other
The height in the region of object contact.
In this specification, as shown in figure 4, " the load area rate Smr1 for separating prominent peak potion and central part " refers to foundation
Upper height that ISO25178 is measured, indicating central part and the load area rate of the intersection point of load curve (separate center
The load area rate in portion and prominent peak potion) parameter.The value is bigger, and the ratio for referring to that prominent peak potion occupies is bigger.It needs to illustrate
, in Fig. 4, Sk indicates the height of central part, and Smr2 indicates to separate the load area rate of central part and prominent valley.Separation is prominent
The load area rate Smr1 of peak potion and central part can be by utilizing commercially available laser microscope to as defined in processing surface out
Measurement area (such as 100 μm2Region) surface profile be measured to calculate.
In this specification, " the vertex density Spd at peak " is to indicate peak measured according to ISO25178, per unit area
The parameter of vertex quantity.Indicate when the value is big more with the quantity of the contact point of other objects.The vertex density Spd at peak can pass through
Using commercially available laser microscope to (such as 100 μm of defined measurement area of processing surface2Region) surface profile into
Row is measured and is calculated.
In this specification, " electrode surface " of electrolytic copper foil refers to when making electrolytic copper foil and the face of cathode contacts side.
In this specification, " face is precipitated " of electrolytic copper foil refers to the face of the cathode copper precipitation side when making electrolytic copper foil,
That is the not face with cathode contacts side.
Surface treatment copper foil
Copper foil of the invention is surface treatment copper foil.The surface treatment copper foil has processing surface at least side.At this
Reason surface is 55mm according to the arithmetic average curvature Spc of the peak maximum measured ISO25178-1More than.In addition, the surface treatment
Resin film hot pressing is being connected to processing surface to handle the transferring surface shape on surface to the surface of resin film by copper foil,
And by etching removal surface treatment copper foil when, remaining resin film (hereinafter also referred to resin replica product) surface (hereinafter,
Also referred to as transfer surface), the arithmetic average curvature Spc of peak maximum that is measured according to ISO25178 be 55mm-1More than.This
Sample assigns the arithmetic average curvature of the peak maximum by being measured according to ISO25178 by the processing surface to surface treatment copper foil
The distinctive surface profile that Spc is limited, being capable of providing when for SAP method can will not only plating circuit excellent adhesion but also right
Also excellent surface profile assigns the surface treatment copper foil of laminated body to the etching of electroless copper.In addition, by using above-mentioned table
Surface treatment copper foil can be realized extremely fine dry film resolution ratio in the dry film developing procedure in SAP method.
Plating circuit adaptation is natively difficult to have both with the etching to electroless copper, but according to the present invention, exceeds pre-
Material ground can have both the two.That is, as previously mentioned, being suitable for improving and the recess portion that there is centre to attenuate of the adaptation of plating circuit
In the process (h) of Fig. 2, the etching of electroless copper is easily reduced surface profile.That is, being filled again to eliminate in electroless copper
Remaining copper is eliminated in the part for the recess portion that the centre of type concaveconvex shape attenuates, and needs more to etch.But using of the invention
Roughening treatment copper foil can realize the reduction of such etch quantity and can ensure excellent plating circuit adaptation.It can recognize
For this is because by the way that the Spc of the processing surface Spc of surface treatment copper foil and the transfer surface of resin replica product are set to
55mm-1More than, to bring the intermediate concaveconvex shape not attenuated.
That is, the vertex of protrusion is sharp when Spc is larger, therefore the intermediate processing surface not attenuated and the intermediate processing to attenuate
Surface is compared, and the vertex of protrusion is sharp, i.e., Spc becomes larger.For the resin replica product transferred with the concaveconvex shape for handling surface
Transfer surface, it may also be said to which when Spc is larger, the vertex of protrusion is sharp.This is because in the case of the intermediate concaveconvex shape to attenuate
The vertex of transfer surface flattens smooth, and the vertex of the transfer surface in the case of the intermediate concaveconvex shape not attenuated is unchanged flat, tool
There is certain curvature (i.e. sharp).As a result, the intermediate transfer surface not attenuated is compared with the transfer surface that centre attenuates, Spc
Become larger.It can think, by Spc points that make the processing surface Spc of surface treatment copper foil and the transfer surface of resin replica product
Indescribably a height of 55mm-1More than, the intermediate concaveconvex shape not attenuated is brought, the above problem due to the intermediate shape to attenuate is suitable
It eliminates sharply.It can think, by the intermediate shape that do not attenuate, electroless copper can be made verily to follow the bumps on processing surface
Shape is simultaneously reproduced without damaging its shape, and as a result, it is possible to realize the excellent adaptation with plating circuit without damaging
To the etching of electroless copper.In such manner, it is possible to take into account plating circuit adaptation and the etching to electroless copper.And it can recognize
For by that can take into account such excellent adaptation and the etching excellent to electroless copper, the dry film in SAP method develops work
In sequence, atomic thin dry film resolution ratio can be realized.Therefore, surface treatment copper foil of the invention is preferred for utilizing SAP method
The production of printed circuit board.In other words, surface treatment copper foil of the invention is preferred for concaveconvex shape being transferred to printed circuit
On the insulating resin layer of plate.
Surface treatment copper foil of the invention has processing surface at least side.Processing surface is to implement at arbitrary surfaces
The face of reason, typically roughening treatment face.In short, surface treatment copper foil can have processing surface (such as coarse in two sides
Change process face), only there can also be processing surface in side.In the case where two sides have processing surface, when being used for SAP method,
The face (face of the face opposite side closely sealed with insulating resin) of laser irradiation side is also surface-treated, therefore laser absorption
Height, as a result laser beam perforation also improves.
The arithmetic average curvature Spc of the peak maximum on the processing surface of surface treatment copper foil of the invention is 55mm-1More than, it is excellent
It is selected as 60mm-1Above and 200mm-1Below, it is more preferably 60mm-1Above and 150mm-1Below.When in such range, hold
Easily realize the intermediate concaveconvex shape not attenuated.
Resin film hot pressing is being connected to processing surface to handle the surface on surface by surface treatment copper foil of the invention
Shape transfer is to the surface of resin film, and when surface treatment copper foil being removed by etching, the surface of remaining resin film
The arithmetic average curvature Spc of the peak maximum of (i.e. the transfer surfaces of resin replica product) is 55mm-1More than, preferably 60mm-1More than
And 200mm-1Below, it is more preferably 60mm-1Above and 150mm-1It below, is more preferably 60mm-1Above and 130mm-1With
Under.When in such range, concaveconvex shape that centre easy to accomplish does not attenuate.The preferred heat-curing resin of resin film is thin
Film can be the form of prepreg.As the example of heat-curing resin, epoxy resin, cyanate ester resin, span can be enumerated
Come acid imide cyanate resin (BT resin), polyphenylene oxide resin, phenolic resin, polyimide resin etc..As long as thermo-compression bonding can incite somebody to action
The concaveconvex shape on the processing surface of surface treatment copper foil carries out under conditions of being transferred to resin film, is not particularly limited.
Such as it preferably carries out being thermally compressed for 60~120 minutes at 3.0~5.0MPa of pressure, 200~240 DEG C of temperature.
Surface (i.e. turn of resin replica product of the surface treatment copper foil of the invention remaining resin film after above-mentioned etching
Print surface) the prominent peak potion of separation and central part load area rate Smr1 be preferably 9.0% or more, more preferably 10~
It 20%, is more preferably 10~15%.When in such range, the intermediate shape not attenuated can be more desirably limited.
As previously mentioned, the value of Smr1 is bigger, refer to that ratio shared by prominent peak potion is bigger.For the point, due to passing through the benefit from top
The intermediate taper portion of the transfer surface of resin replica product is not detected with the observation of laser microscope, therefore in laser microscope
Middle understanding can be recognized as the equivalence of the rectangle imagination transfer surface with the intermediate rectangular-shaped recess portion not attenuated by laser microscope
Object.As a result, the increment rate of sectional area when being cut into disk since top becomes constant immediately, i.e., prominent peak potion becomes smaller, as a result
Smr1 becomes smaller.In contrast, (it turns with aforementioned rectangular imagination for the intermediate transfer surface not attenuated and the intermediate transfer surface to attenuate
Print surface is of equal value) it compares, prominent peak potion is bigger, and therefore, Smr1 becomes larger.That is, the intermediate processing surface not attenuated and centre attenuate
Processing surface compare, ratio shared by prominent peak potion becomes larger, i.e., Smr1 becomes larger.
Preferred embodiment according to the present invention is attached with multiple roughening particles on processing surface.That is, processing surface is excellent
It is selected as roughening treatment face.Roughening particle is preferably formed by copper particle.Copper particle can be formed by metallic copper, can also be by copper
Alloy is formed.But copper particle be copper alloy in the case where, sometimes relative to copper etchant solution dissolubility reduce or because alloy at
Divide the service life reduction for being mixed into and leading to etching solution into copper etchant solution, therefore preferably copper particle is formed by metallic copper.
Processing surface is preferably 5000mm according to the vertex density Spd at the peak measured ISO25178-2Above and
20000mm-2Below, it is more preferably 7000mm-2Above and 18000mm-2It below, is more preferably 10000mm-2Above and
15000mm-2Below.When in the range, the anchoring effect based on concaveconvex shape, plating circuit adaptation can be given full play to
And dry film resolution ratio improves.
The thickness of surface treatment copper foil of the invention is not particularly limited, preferably 0.1~18 μm, more preferably 0.5
~10 μm, further preferably 0.5~7 μm, particularly preferably 0.5~5 μm, most preferably 0.5~3 μm.It should be noted that
Surface treatment copper foil of the invention is not limited to carry out the surface of common copper foil the surface treatments such as roughening treatment and winner,
It can be to have carried out the surface treatments such as roughening treatment and winner to the copper foil surface with carrier copper foil.
The manufacturing method of surface treatment copper foil
An example of the preferable production process of surface treatment copper foil of the invention is illustrated, but surface treatment of the invention
Copper foil is not limited to method described below, as long as can be realized the surface profile of surface treatment copper foil of the invention, can pass through
The manufacture of one blanking method.
(1) preparation of copper foil
Copper foil used in manufacture as surface treatment copper foil, can be used both electrolytic copper foil and rolled copper foil.
The thickness of copper foil is not particularly limited, preferably 0.1~18 μm, more preferably 0.5~10 μm, further preferably 0.5~7
μm, particularly preferably 0.5~5 μm, be most preferably 0.5~3 μm.In the case where preparing copper foil in the form of with carrier copper foil, copper
Foil can by the dry types such as the wet type membrane formations such as electroless copper method and copper electroplating method, sputtering and chemical vapor deposition membrane formation process or
Their combination is formed.
(2) it is surface-treated (roughening treatment)
It is roughened using at least one surface of copper particle to copper foil.The roughening is by using roughening treatment
It is carried out with the electrolysis of cupric electrolysis solution.Plating process of the electrolysis preferably through 2 stages carries out.In the plating process in the 1st stage
In, it is preferable to use the copper-bath comprising 200~280g/L of 8~12g/L of copper concentration and sulfuric acid concentration, in liquid temperature 20~40
DEG C, 15~35A/dm of current density2, carry out electro-deposition under the time 5~25 seconds plating conditions.The plating process in the 1st stage
Amount to 2 times it is preferable to use 2 slots.In the plating process in the 2nd stage, it is preferable to use comprising 65~80g/L of copper concentration and
The copper-bath of 200~280g/L of sulfuric acid concentration, in 45~55 DEG C of liquid temperature and 5~30A/dm of current density2, the time 5~25
Electro-deposition is carried out under the plating conditions of second.The electricity in each stage is preferably with the electricity Q in the plating process in the 1st stage1Relative to
Electricity Q in the plating process in the 2nd stage2Ratio (Q1/Q2) mode less than 1.0 set, more preferably 0.5~0.9,
Further preferably 0.7~0.9.In this way by reducing Q1/Q2, can be realized and have the coarse of the intermediate concaveconvex shape not attenuated
Change process face.It should be noted that the electricity Q when plating process in the 1st stage carries out multiple1For the total electricity of multiple process.
(3) antirust treatment
According to expectation, antirust treatment can be implemented to the copper foil after roughening treatment.Antirust treatment preferably includes to use
The plating of zinc.The plating for having used zinc can be any one of zinc-plated processing and galvanized alloy processing；Zinc-plated conjunction
In gold processing, particularly preferred zinc-nickel alloy processing.As long as zinc-nickel alloy processing is including at least the plating of Ni and Zn
Can, the other elements such as Sn, Cr, Co can also be included.Ni/Zn attachment ratio in zinc-nickel alloy plating is preferred by quality ratio
It is 1.2~10, more preferably 2~7, further preferably 2.7~4.In addition, antirust treatment preferably also includes chromic acid salt treatment,
The chromic acid salt treatment carries out the surface of the coating comprising zinc more preferably after the plating for having used zinc.In this way, energy
Enough further increase rust-preventing characteristic.Particularly preferred antirust treatment is the group for plating zinc-nickel alloy processing and chromic acid salt treatment thereafter
It closes.
(4) silane coupling agent is handled
According to expectation, silane coupling agent processing can be implemented to copper foil, form silane coupling agent layer.Thereby, it is possible to improve
Moisture-proof, chemical reagent resistance and with the adaptation of bonding agent etc. etc..Silane coupling agent layer can by silane coupling agent into
Row acceptable diluent is simultaneously coated and dried to be formed.It as the example of silane coupling agent, can enumerate: 4- glycidyl butyl three
Silanes' coupling agents such as methoxy silane, 3- glycidoxypropyltrime,hoxysilane；Or 3- aminopropyl three
Ethoxysilane, N-2 (amino-ethyl) 3- TSL 8330, N-3- (4- (3- amino propoxyl group) butoxy) third
The amino-functional silanes such as base -3- TSL 8330, N- phenyl -3- TSL 8330 coupling
Agent；Or the Mercaptofunctionals such as 3-mercaptopropyi trimethoxy silane silane coupling agent or vinyltrimethoxysilane, vinyl
The alkene functional silanes coupling agent such as phenyltrimethoxysila,e；Or 3- methacryloxypropyl trimethoxy silane etc. third
Olefin(e) acid class functional silanes coupling agent；Or the imidazoles functional silanes coupling agent such as imidizole silane；Or the triazines function such as triazine silane
Property silane coupling agent etc..
Band carrier copper foil
Surface treatment copper foil of the invention can provide in the form of with carrier copper foil.In this case, having with carrier copper foil
It is standby: carrier；The peeling layer being set on the carrier；And to handle surface (typically roughening treatment on the peeling layer
Face) surface treatment copper foil of the invention that is arranged as outside.Certainly, of the invention in addition to using for band carrier copper foil
Other than surface treatment copper foil, it can also be constituted using well known layer.
Carrier is to be used to support thick surface treatment copper foil to improve the layer (typically foil) of its treatability.As carrier
Example, aluminium foil, copper foil, resin film etc. that metal coating has been carried out to surface, preferably copper foil can be enumerated.Copper foil can be with
For any one in rolled copper foil and electrolytic copper foil.For 200 μm hereinafter, preferably 12 μm~35 μm for the thickness of carrier is typical.
The face of the peeling layer side of carrier preferably has 0.5~1.5 μm of 10 surface roughness Rzjis, and more preferably 0.6
~1.0 μm.Rzjis can be determined according to JIS B 0601:2001.This is assigned in advance by the face of the peeling layer side to carrier
10 surface roughness Rzjis of sample, can be easy to the surface treatment copper of the invention made on it by peeling layer
Foil assigns ideal surface profile.
Peeling layer is with the peel strength for weakening carrier, the stability for ensuring the intensity and then to inhibit at high temperature
When compression moulding can between carrier and copper foil the function of caused phase counterdiffusion layer.For peeling layer, usually in carrier
One face is formed, and can also be formed on two sides.Peeling layer can be any one in organic peeling layer and inorganic release layer.As having
The example of organic principle used in machine peeling layer can enumerate: organic compounds containing nitrogen, organic compounds containing sulfur, carboxylic acid
Deng.It as the example of organic compounds containing nitrogen, can enumerate: triazole compounds, imidazolium compounds etc., wherein triazole compounds
It is preferred in terms of fissility is easy stable.As the example of triazole compounds, can enumerate: 1,2,3- benzotriazole,
Carboxyl benzotriazole, N ', bis- (benzotriazole ylmethyl) ureas of N ' -, 1H-1,2,4- triazole and 3- amino -1H-1,2,4- triazole
Deng.It as the example of organic compounds containing sulfur, can enumerate: mercaptobenzothiazoler, thio cyanuric acid, 2- benzimidazole mercaptan
Deng.As the example of carboxylic acid, monocarboxylic acid, dicarboxylic acids etc. can be enumerated.On the other hand, as nothing used in inorganic release layer
The example of machine ingredient can enumerate: Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate film etc..It should be noted that right
In the formation of peeling layer, if by make carrier at least one surface contact containing removing composition of layer solution, by peeling layer at
Divide and is fixed on the progress such as surface of carrier.Carrier with containing removing composition of layer solution contact by containing removing composition of layer
The dipping of solution, the spraying of solution of the composition of layer containing removing, the composition of layer containing removing flowing down etc. for solution carry out.Separately
Outside, fixation of the removing composition of layer to carrier surface passes through the absorption of solution of the composition of layer containing removing, drying, the composition of layer containing removing
The electro-deposition etc. of removing composition of layer in solution carries out.It is 1nm~1 μm for the thickness of peeling layer is typical, preferably 5nm
~500nm.
As surface treatment copper foil, the surface treatment copper foil of aforementioned present invention is used.Surface treatment copper foil allusion quotation of the invention
Surface treatment copper foil made of the roughened processing of copper particle is used to type for implementation, as step, first in peeling layer
Surface layers of copper is formed in the form of copper foil, be then at least roughened.About roughened details, such as preceding institute
It states.It should be noted that the advantages of copper foil preferably should be using as with carrier copper foil, with the morphosis of ultrathin copper foil.Make
For the preferred with a thickness of 0.1 μm~7 μm, more preferably 0.5 μm~5 μm, further preferably 0.5 μm~3 μm of ultrathin copper foil.
Other function layer can be set between peeling layer and copper foil.As the example of such other function layer, can arrange
Enumerate auxiliary metal layer.Auxiliary metal layer is preferably formed by nickel and/or cobalt.The thickness of auxiliary metal layer is preferably set to 0.001~3
μm。
Copper-clad laminated board
Surface treatment copper foil of the invention or the production for being preferred for printed circuit board copper-clad laminated board with carrier copper foil.
That is, according to the preferred embodiment of the present invention, providing a kind of manufacturing method of copper-clad laminated board, which is characterized in that using above-mentioned
Surface treatment copper foil or above-mentioned band carrier copper foil manufacture copper-clad laminated board, or provide and use above-mentioned surface treatment copper foil or above-mentioned
Copper-clad laminated board obtained from band carrier copper foil.By using surface treatment copper foil of the invention or with carrier copper foil, so as to
Enough copper-clad laminated boards provided particularly suitable for SAP method.The copper-clad laminated board has: band carrier copper foil of the invention and being sealed at
The processing surface and the resin layer being arranged.The single side in resin layer can be set with carrier copper foil, also can be set in two sides.Tree
Rouge layer includes resin, preferably insulative resin.Resin layer is preferably prepreg and/or resin sheet.Prepreg is to make synthetic resin
It is infiltrated in the general name of composite material obtained from the substrates such as synthetic resin board, glass plate, glass woven fabric, glass non-woven fabric, paper.Make
It for the preferred example of insulative resin, can enumerate: epoxy resin, cyanate ester resin, bismaleimide-triazine resin (BT tree
Rouge), polyphenylene oxide resin, phenolic resin etc..In addition, the example as the insulative resin for constituting resin sheet, can enumerate: epoxy
The insulating resins such as resin, polyimide resin, polyester resin.It can be in addition, from the viewpoints such as insulating properties are improved, in resin layer
Contain the filler particles etc. comprising the various inorganic particles such as silica, aluminium oxide.The thickness of resin layer is not particularly limited,
Preferably 1~1000 μm, more preferably 2~400 μm, further preferably 3~200 μm.Resin layer can be made of multiple layers.
The resin layers such as prepreg and/or resin sheet can also be set to band by the primer resin layer being pre-coated in copper foil surface and carry
Body copper foil.
Printed circuit board
Surface treatment copper foil of the invention or the production for being preferred for printed circuit board with carrier copper foil, particularly preferred for
Utilize the production of the printed circuit board of SAP method.That is, according to the preferred embodiment of the present invention, it is possible to provide a kind of printed circuit board
Manufacturing method, which is characterized in that using aforementioned surfaces processing copper foil or above-mentioned band carrier copper foil manufacture printed circuit board, or
It provides using printed circuit board obtained from aforementioned surfaces processing copper foil or above-mentioned band carrier copper foil.By using table of the invention
Surface treatment copper foil or with carrier copper foil, in the manufacturing of printed circuit boards can will not only plating circuit adaptation so as to provide
Surface treatment copper foil excellent and that laminated body is assigned to the etching of electroless copper also excellent surface profile.In addition, passing through
Using above-mentioned surface treatment copper foil, to can be realized extremely fine dry film in the dry film developing procedure in SAP method and differentiate
Rate.Therefore, it is capable of providing and implements the printed circuit board that extremely fine circuit is formed.The printed circuit board packet of present embodiment
It is constituted containing the layer for being sequentially laminated with resin layer, layers of copper.In the case where SAP method, since surface treatment copper foil of the invention is Fig. 1's
Be removed in process (c), thus by the printed circuit board that SAP method makes be free of surface treatment copper foil of the invention,
Only remain the surface profile from the processing surface transfer of surface treatment copper foil.In addition, for resin layer, such as above in connection with copper clad layers
Described in lamination.In any case, printed circuit board can be constituted using well known layer.As the tool in relation to printed circuit board
Body example can enumerate: being bonded surface treatment copper foil of the invention in the one or two sides of prepreg and solidify and laminated body is made
On the basis of, carry out one or two sides printed circuit board obtained from circuit formation；Multilayer made of multiple stratification is carried out to them
Printed circuit board etc..In addition, can also enumerate as other concrete examples and form surface treatment of the invention on resin film
Copper foil and formed the flexible printed circuit board of circuit, COF, TAB band etc..In turn, it as other concrete examples, can enumerate: to this
The surface treatment copper foil of invention is coated with above-mentioned resin layer and forms the copper foil (RCC) with resin, using resin layer as insulation
After layer of adhesive material is laminated in above-mentioned printed base plate, pass through surface treatment copper foil as all or part of of wiring layer
The methods of MSAP method, method of residues form the build-up wiring plate of circuit, remove surface treatment copper foil and form electricity by SAP method
The build-up wiring plate on road；The stacking and circuit that the copper foil with resin is alternately repeated on semiconductor integrated circuit form straight
Connect lamination wafer (direct buildup on wafer) etc..It as the concrete example further developed, can also enumerate: will
The above-mentioned copper foil with resin is laminated in substrate and carries out antenna element obtained from circuit formation；It is laminated in by adhesive layer
Glass, resin film and the panel/display electronic material, the glass pane electronic material that form pattern；Of the invention
Electromagnetic wave shielding/film etc. made of applying conductive bonding agent on surface treatment copper foil.Band carrier copper foil of the invention is special
Suitable for SAP method.For example, composition shown in Fig. 1 and 2 can be used in the case where carrying out circuit formation by SAP method.
[embodiment]
By example below, more specifically the present invention will be described.
Example 1 and 2
Copper foil is handled as band carrier surface, production with carrier roughening treatment copper foil and is evaluated as follows.
(1) production of carrier
The copper-bath of composition as shown below is used as copper electrolyte；Use arithmetical average surface thick as cathode
The rotation electrode for the titanium that rugosity Ra (according to JIS B 0601:2001) is 0.20 μm；Anode uses DSA (dimensional stability sun
Pole), in 45 DEG C of solution temperature, current density 55A/dm2Under be electrolysed, obtain 12 μm of thickness of electrolytic copper foil as carrier.
10 mean roughness Rzjis in the face of the peeling layer side of resulting vehicle are measured according to JIS B 0601:2001, as a result
It is 0.9 μm.
<composition of copper-bath>
Copper concentration: 80g/L
Sulfuric acid concentration: 260g/L
Bis- (3- sulfopropyl) disulphide concentration: 30mg/L
Diallyldimethylammonium chloride polymer concentration: 50mg/L
Cl concn: 40mg/L
(2) formation of peeling layer
The electrode surface side of carrier copper foil through pickling processes is dense in CBTA (carboxyl benzotriazole) concentration 1g/L, sulfuric acid
It spends in the CBTA aqueous solution of 150g/L and copper concentration 10g/L, impregnated 30 seconds at 30 DEG C of liquid temperature, CBTA ingredient is made to be adsorbed in load
The electrode surface of body.In this way, using the surface of the electrode surface of copper foil to form CBTA layers as organic peeling layer in carrier.
(3) formation of auxiliary metal layer
The carrier for being formed with organic peeling layer is impregnated in the molten of the nickel concentration 20g/L made using nickel sulfate with copper foil
In liquid, in 45 DEG C of liquid temperature, pH3, current density 5A/dm2Under conditions of, keep the nickel for being equivalent to 0.001 μm of thickness of adhesion amount attached
In on organic peeling layer.Nickel layer is formed in this way on organic peeling layer as auxiliary metal layer.
(4) ultrathin copper foil is formed
The carrier for being formed with auxiliary metal layer is impregnated in the copper-bath of composition as shown below with copper foil, in solution
Temperature 50 C, 5~30A/dm of current density2Under be electrolysed, formd in auxiliary metal layer 3 μm of thickness (example 1,3 and 4) or
The ultrathin copper foil of 2.5 μm (example 2).
<composition of solution>
Copper concentration: 60g/L
Sulfuric acid concentration: 200g/L
(5) roughening treatment
The precipitation face of above-mentioned ultrathin copper foil is roughened.The roughening treatment passes through following 2 stage plating
It carries out.The plating process in the 1st stage amount to 2 times using 2 slots, in each plating process (i.e. each slot), using including copper
The copper-bath of 230~250g/L of concentration 10.8g/L and sulfuric acid concentration, in 25 DEG C of solution temperature, current density 25A/dm2's
Electro-deposition is carried out under plating conditions.In the plating process in the 2nd stage, using comprising copper concentration 70g/L and sulfuric acid concentration 230~
The copper-bath of 250g/L, in 50 DEG C of solution temperature and current density 58A/dm2Plating conditions under carry out electro-deposition.Each rank
The electricity of section is with the electricity Q in the plating process in the 1st stage1Relative to the electricity Q in the plating process in the 2nd stage2Ratio (Q1/
Q2) set less than the mode of 1 (specifically 0.87).Electro-deposition is carried out under the conditions of specifically each shown in the table 1.
(6) antirust treatment
The two sides with carrier copper foil after roughening treatment is carried out anti-comprising inorganic antirust treatment and chromic acid salt treatment
Rust processing.Firstly, being bathed as inorganic antirust treatment using pyrophosphoric acid, in potassium pyrophosphate concentration 80g/L, zinc concentration 0.2g/L, nickel
Concentration 2g/L, 40 DEG C of liquid temperature, current density 0.5A/dm2Lower progress zinc-nickel alloy antirust treatment.Then, at as chromate
Reason on the basis of zinc-nickel alloy antirust treatment, and then forms chromate coating.The chromic acid salt treatment chromic acid concentration be 1g/L,
PH11,25 DEG C of solution temperature, current density 1A/dm2Lower progress.
(7) silane coupling agent is handled
The copper foil for implementing above-mentioned antirust treatment is washed, silane coupling agent processing is carried out immediately after, makes silane
Coupling agent is adsorbed on the antirust treatment layer in roughening treatment face.Silane coupling agent processing is following to be carried out: by using pure water
As solvent, the solution that 3- TSL 8330 concentration is 3g/L, the solution is blown into slightly in a manner of spray
Roughening process face carries out adsorption treatment.After the absorption of silane coupling agent, finally evaporate moisture using electric heater, to obtain
The band carrier copper foil for having 3 μm of thickness (example 1,3 and 4) or 2.5 μm (example 2) of roughening treatment copper foil.
(8) evaluation of roughening treatment copper foil
Each characteristic of surface profile comprising roughening particle is evaluated gained roughening treatment copper foil as follows.
<Spc and Spd of roughening treatment copper foil>
Utilize laser method for roughening treatment using laser microscope (KEYENCE CORPORATION system, VK-X100)
100 μm of the area in the roughening treatment face of copper foil2The surface profile of 2 dimensional region (10 10 μm of μ m) parsed, foundation
Arithmetic average curvature Spc (mm of the ISO25178 to the peak maximum in the roughening treatment face of roughening treatment copper foil-1) and peak top
Dot density Spd (mm-2) be measured.The cutoff wavelength obtained using S filter is set as 0.8 μm, will be filtered using L by the measurement
The cutoff wavelength that device obtains is set as 0.1 μm to carry out.Same sample is carried out to amount to 3 said determinations, using being averaged for they
Value is used as measured value.
<Spc and Smr1 on resin replica product surface>
The replica shape that the surface profile in the roughening treatment face of roughening treatment copper foil is made of resin, to gained resin
The surface profile on replica product surface is parsed.Specifically, firstly, to prepreg (Mitsubishi Gas Chemical Co., Ltd's system,
GHPL-830NS, thickness 0.1mm) it is laminated in a manner of with its ultrathin copper foil side contacts of carrier copper foil, in pressure 4.0MPa, temperature
It carries out being thermally compressed for 90 minutes at 220 DEG C.Thereafter, carrier is removed, it is with chlorination copper system etching solution that the ultrathin copper foil through crimping is complete
Removal, obtains the resin replica product transferred with the surface profile in roughening treatment face.Use laser microscope (KEYENCE
CORPORATION system, VK-X100) utilize laser method (to transfer the table in roughening treatment face to the transfer surface of the resin replica product
The face of facial contour) 100 μm of area2The surface profile of 2 dimensional region (10 10 μm of μ m) parsed, according to ISO25178
To the arithmetic average curvature Spc (mm of the peak maximum on resin replica product surface-1) and separate the load surface of prominent peak potion and central part
Product rate Smr1 (%) is measured.The cutoff wavelength obtained using S filter is set as 0.8 μm, will utilize L filter by the measurement
Obtained cutoff wavelength is set as 0.1 μm to carry out.Same sample is carried out to amount to 3 said determinations, using their average value
As measured value.
(9) production of copper-clad laminated board
Copper-clad laminated board is made using band carrier copper foil.Firstly, on the surface of internal substrate by prepreg (Mitsubishi's gas
Chemical Co., Ltd. system, GHPL-830NSF, thickness 0.1mm) laminated belt carrier copper foil ultrathin copper foil, in pressure 4.0MPa, temperature
After carrying out 90 minutes thermo-compression bonding at 220 DEG C of degree, carrier is removed, makes copper-clad laminated board.
(10) the SAP evaluation production of laminated body
Then, after all being removed the copper foil on surface with sulfuric acid/hydrogen peroxide system etching solution, degreasing, the catalysis of Pd system are carried out
Agent is assigned and is activated.Electroless copper (thickness: 1 μm) is carried out to the surface through activating in this way, obtaining will in SAP method
Laminated body (hereinafter referred to as SAP evaluation laminated body) before pasting dry film.These processes according to the well known condition of SAP method into
Row.
(11) the SAP evaluation evaluation of laminated body
To above-mentioned gained SAP evaluation laminated body, it is proceed as follows the evaluation of various characteristics.
<plating circuit adaptation (peel strength)>
Make dry film pasting in SAP evaluation laminated body, is exposed and develops.Pass through pattern plating being done after development
After 19 μm of thickness of layers of copper is precipitated in the laminated body of film masking, dry film is removed.It will be showed with sulfuric acid hydrogen peroxide system etching solution
Electroless copper removal, 20 μm of height, the peel strength test sample of width 10mm is made.According to JIS C 6481
(1996), peel strength when removing copper foil from sample for evaluation is measured.
<etching>
It carries out 0.2 μm every time of etching with laminated body to SAP evaluation with sulfuric acid/hydrogen peroxide system etching solution, measures surface
Copper completely disappear until amount (depth).For measurement method, confirmed with optical microscopy (500 times).More specifically,
Every operation for carrying out confirming the presence or absence of copper when 0.2 μm of etching by optical microscopy is repeated, using by (number of etching) × 0.2
μm index of the obtained value (μm) as etching.Refer to for example, etching is 1.2 μm, when carrying out 6 0.2 μm of etchings, uses
Optical microscopy can't detect remaining copper (i.e. 6 times=1.2 μm of 0.2 μ m).That is, the value is smaller, it more can be with fewer number
Etching removes the copper on surface.Refer to: the value is smaller, etching is the better.
<dry film resolution ratio (minimum L/S)>
The dry film that 25 μm of thickness are pasted on the surface of SAP evaluation laminated body is 2 using line/interval (L/S) is formd
μm/mask of 2 μm to 15 μm/15 μm of pattern, it is exposed and develops.Light exposure at this time is set as 125mJ.Use optical microphotograph
The surface of sample after (500 times) of mirror observation developments, using can be the smallest (i.e. most in the L/S that there is no problem develops
Fine) index of the L/S as dry film resolution ratio.For example, minimum L/S=10 μm of the index as the evaluation of dry film resolution ratio/
10 μm refer to, until L/S=15 μm/15 μm to 10 μm/10 μm, without problem differentiate.For example, without problem
In the case that ground is differentiated, striking contrast degree is observed between dry film pattern, the feelings that cannot be differentiated well in contrast
Under condition, black part is observed between dry film pattern, does not observe striking contrast degree.
Example 3(comparison)
With the electricity Q in roughening treatment, the 1st stage plating process1In plating process relative to the 2nd stage
Electricity Q2Ratio (Q1/Q2) set as 2.16 mode and (carry out electricity under the conditions of specifically each shown in the table 1 to sink
Product), it in addition to this, is operated in the same way with the step described in example 1, carries out the production with carrier roughening treatment copper foil and comment
Valence.
Example 4(comparison)
With the electricity Q in roughening treatment, the 1st stage plating process1In plating process relative to the 2nd stage
Electricity Q2Ratio (Q1/Q2) set as 3.38 mode and (carry out electricity under the conditions of specifically each shown in the table 1 to sink
Product), it in addition to this, is operated in the same way with the step described in example 1, carries out the production with carrier roughening treatment copper foil and comment
Valence.
As a result
Evaluation result obtained in example 1~4 is as shown in table 2.
[table 1]
[table 2]
Claims (10)
1. a kind of surface treatment copper foil is the surface treatment copper foil for having processing surface at least side,
The processing surface is 55mm according to the arithmetic average curvature Spc of the peak maximum measured ISO25178-1More than,
Resin film hot pressing is connected to the processing surface thus by the transferring surface shape on the processing surface to the resin
The surface of film, and by etching by the surface treatment copper foil remove when, the surface of the remaining resin film
Arithmetic average curvature Spc according to the peak maximum measured ISO25178 is 55mm-1More than.
2. surface treatment copper foil according to claim 1, wherein the institute of the remaining resin film after the etching
The load area rate Smr1 for stating surface is measured according to ISO25178, the prominent peak potion of separation and central part is 9.0% or more.
3. surface treatment copper foil according to claim 1 or 2, wherein be attached with roughening particle on the processing surface.
4. surface treatment copper foil described in any one of claim 1 to 3, wherein processing surface foundation
The vertex density Spd at the peak that ISO25178 is measured is 5000mm-2Above and 20000mm-2Below.
5. surface treatment copper foil according to any one of claims 1 to 4, wherein the surface treatment copper foil has 0.5
~5 μm of thickness.
6. surface treatment copper foil according to any one of claims 1 to 5 is used to for concaveconvex shape being transferred to printing electricity
The insulating resin layer of road plate.
7. surface treatment copper foil described according to claim 1~any one of 6 is used for the printed circuit based on semi-additive process
The production of plate.
8. a kind of band carrier copper foil, has:
Carrier；
The peeling layer being set on the carrier；And
The surface according to any one of claims 1 to 7 being arranged using the processing surface on the outside of on the peeling layer
Handle copper foil.
9. a kind of manufacturing method of copper-clad laminated board, which is characterized in that use surface described in any one of claim 1~7
Copper foil or band carrier copper foil according to any one of claims 8 are handled to manufacture copper-clad laminated board.
10. a kind of manufacturing method of printed circuit board, which is characterized in that use surface described in any one of claim 1~7
Copper foil or band carrier copper foil according to any one of claims 8 are handled to manufacture printed circuit board.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-081447 | 2016-04-14 | ||
| JP2016081447 | 2016-04-14 | ||
| PCT/JP2017/012678 WO2017179416A1 (en) | 2016-04-14 | 2017-03-28 | Treated surface copper foil, copper foil with carrier as well as methods for manufacturing copper-clad laminate and printed circuit board using same |
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| Publication Number | Publication Date |
|---|---|
| CN109072472A true CN109072472A (en) | 2018-12-21 |
| CN109072472B CN109072472B (en) | 2020-10-16 |
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| CN201780023464.6A Active CN109072472B (en) | 2016-04-14 | 2017-03-28 | Surface-treated copper foil, copper foil with carrier, and copper-clad laminate and printed wiring board manufacturing method using same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP6945523B2 (en) |
| KR (1) | KR102338103B1 (en) |
| CN (1) | CN109072472B (en) |
| MY (1) | MY186859A (en) |
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| CN112004964A (en) * | 2018-04-25 | 2020-11-27 | 古河电气工业株式会社 | Surface-treated copper foil, copper-clad plate and printed circuit board |
| CN112424399A (en) * | 2018-08-10 | 2021-02-26 | 三井金属矿业株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
| CN113811641A (en) * | 2019-05-15 | 2021-12-17 | 住友电气工业株式会社 | Printed wiring board |
| TWI756039B (en) * | 2020-02-04 | 2022-02-21 | 日商三井金屬鑛業股份有限公司 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
| TWI756038B (en) * | 2020-02-04 | 2022-02-21 | 日商三井金屬鑛業股份有限公司 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
| CN114761622A (en) * | 2019-12-13 | 2022-07-15 | Ｊｘ金属株式会社 | Surface-treated copper foil, copper-clad laminate, and printed wiring board |
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| KR102231993B1 (en) * | 2018-03-28 | 2021-03-25 | 미쓰이금속광업주식회사 | Manufacturing method of multilayer wiring board |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6945523B2 (en) | 2021-10-06 |
| JPWO2017179416A1 (en) | 2019-02-21 |
| TWI711139B (en) | 2020-11-21 |
| WO2017179416A1 (en) | 2017-10-19 |
| CN109072472B (en) | 2020-10-16 |
| KR20180133845A (en) | 2018-12-17 |
| KR102338103B1 (en) | 2021-12-10 |
| MY186859A (en) | 2021-08-26 |
| TW201742212A (en) | 2017-12-01 |
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