CN103476198B - Copper foil for printed circuit board and its preparation method and the printed circuit board (PCB) using the copper foil - Google Patents
Copper foil for printed circuit board and its preparation method and the printed circuit board (PCB) using the copper foil Download PDFInfo
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- CN103476198B CN103476198B CN201310223952.5A CN201310223952A CN103476198B CN 103476198 B CN103476198 B CN 103476198B CN 201310223952 A CN201310223952 A CN 201310223952A CN 103476198 B CN103476198 B CN 103476198B
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- copper foil
- printed circuit
- circuit board
- copper
- etching
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Classifications
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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
- H05K3/10—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
-
- 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
- H05K3/02—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
- H05K3/06—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 the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- 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
Abstract
The present invention provides a kind of copper foil for printed circuit board and its preparation method and the printed circuit board (PCB) using the copper foil, and the cementability between the copper foil for printed circuit board and insulating substrate is good, and can be readily removable by etching from the surface of insulating substrate.The value of closely sealed enhancing coefficient E shown in the below general formula (1) at least one surface of the copper foil for printed circuit board of the present invention is 10 points of height ... (1) of nao-and micro relief of surface area/copper foil surface of 2.5~8, E=copper foil.Wherein, the surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the value that the surface area of copper foil obtains when being and observing the surface of the copper foil using PSTM.
Description
Related application
The application is the Shen with the claim of priority of the Paris Convention based on Japanese patent application 2012-128737
Please.Therefore, the application includes whole items disclosed in the Japanese patent application.
Technical field
The present invention relates to copper foil for printed circuit board, more specifically, is related to the printed circuit board (PCB) for electronic equipment etc.
With copper foil and its manufacture method and the printed circuit board (PCB) using the copper foil.
Background technology
In recent years, with the miniaturization, lightweight and high performance of electronic equipment, tight demand printed circuit board wiring pattern
Become more meticulous.Printed circuit board (PCB) is used for such as semiconductor mounting substrate, motherboard substrate.
At present, as the method for forming thin copper film pattern on a printed circuit, it is known to subtractive process and semi-additive process.
In subtractive process, the surface laminated copper foil first in insulating substrate.Then, resist layer is formed in copper foil surface,
On the resist layer pattern is formed using photoetching process.Then, etching removes the part of the unused resist layer covering of copper foil, is consequently formed
Thin copper film pattern.
In semi-additive process, the thin metal layer for being referred to as crystal seed layer is formed on the surface of insulating substrate first.Then, in crystalline substance
Kind layer surface forms resist layer, and pattern is formed on the resist layer by photoetching process.Then, by the unused against corrosion of crystal seed layer
Implement electro-coppering and form thin copper film pattern in the part of layer covering.The copper-plated part that is not carried out of crystal seed layer is removed by etching.
In semi-additive process, crystal seed layer using electrolytic copper foil or rolled copper foil to be formed when, a surface of copper foil (with
Insulating substrate contacts the surface of side) implement roughening processing.If the surface of copper foil is roughened, formed on the surface of copper foil
Trickle convex portion.By making the convex portion stretch into the inside of insulating substrate, physical anchoring effect can be played, makes copper foil firm
It is adhered to the surface of insulating substrate.
But problems be present in existing printed circuit board (PCB).In semi-additive process, the roughening journey of copper foil surface
When spending big, the inside of insulating substrate is excessively goed deep into the convex portion of copper foil surface.In this case, copper removal is removed from the surface of insulating substrate
Etching period required for paper tinsel (crystal seed layer) is elongated.In addition, the elongated result of etching period is subtracting for the line width of thin copper film pattern
It is a small amount of to become big, therefore become to be difficult to form trickle thin copper film pattern.
On the other hand, it is bonding between copper foil and insulating substrate when the roughening degree on copper foil (crystal seed layer) surface is too small
Property be deteriorated, therefore copper foil becomes prone to the sur-face peeling from insulating substrate, it becomes difficult to forms trickle thin copper film pattern.
Prior art as the surface roughness on copper foil, it is known to following technology.In Japanese Unexamined Patent Publication 07-
In No. 231152 publications (patent document 1), the copper foil that a kind of surface roughness is 1~3 μm is disclosed.The surface of the copper foil is set
There is the trickle pimple of the anti-teardrop shaped that length is 0.6~1.0 μm, maximum gauge is 0.2~0.8 μm.Japanese Unexamined Patent Publication 2006-
A kind of copper foil, the surface roughness (Rz of the copper foil are disclosed in No. 210689 publications (patent document 2)：Nao-and micro relief ten
Point height) it is less than 2.5 μm, the roughening process layer that there is the spheroidal particle by a diameter of 0.05~1.0 μm to form, this is coarse
Change in process layer with least one antirust coat formed above by Mo, Ni, W, P, Co, Ge and with silane coupling layer.Day
A kind of copper foil is disclosed in this JP 2004-263300 publications (patent document 3), the surface roughness (Rz) of the copper foil is
Less than 2.5 μm, distance is more than 5 μm between the minimum peak at matrix peak, and surface has the crystal grain that average grain diameter is less than 2 μm.
In Japanese Unexamined Patent Publication 2010-236058 publications (patent document 4), it is less than 85 degree to disclose a kind of overhead angle, θ that includes
Overshooting shape trickle copper particle copper foil.A kind of copper is disclosed in Japanese Unexamined Patent Publication 10-265872 publications (patent document 5)
Or Cu alloy material, the material utilize calculation of the electron beam three-dimensional roughness resolver based on the surface for being extended to 1000 times
Art mean roughness is 0.05~0.8 μm, and it is 1.005~1.08 that surface area, which replaces value,.
The content of the invention
However, when copper foil of the discovery such as the present inventor disclosed in by patent document 1~5 is adhered to insulating substrate, copper foil
The inside of insulating substrate is excessively goed deep into the convex portion on surface, therefore the etching period required for removal copper foil is elongated.As a result, copper cloth
The reduction quantitative change of line pattern line width is big, therefore becomes to be difficult to form trickle thin copper film pattern.
It is good it is an object of the invention to provide a kind of cementability between insulating substrate and can be by etching from exhausted
The copper foil for printed circuit board and the printed circuit board (PCB) using the copper foil that the surface of edge base material is readily removable.
It is of the invention as described below.
1. a kind of copper foil for printed circuit board, wherein, the closely sealed enhancing system shown in the below general formula (1) at least one surface
Number E value is 2.5~8,
10 points of height (1) of nao-and micro relief of surface area/copper foil surface of E=copper foils
(surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of the copper foil using PSTM.)
2. according to the copper foil for printed circuit board described in above-mentioned 1, wherein, the surface of foregoing copper foil is etched processing.
3. according to the copper foil for printed circuit board described in above-mentioned 2, wherein, the foregoing copper foil surface shown in below general formula (2)
Etch quantity be less than 1 μm,
Etch quantity [μm]=(quality of copper foil after quality-etching of copper foil before etching)/(etch the close of area × copper
Degree) (2)
(in formula, the density of copper is 8.96g/cm3。)
4. according to the copper foil for printed circuit board described in above-mentioned 2 or 3, wherein, the liquid combination used in foregoing etching process
Thing includes more than a kind in the group being made up of hydrogen peroxide, sulfuric acid, halide ion and four azoles.
5. according to the copper foil for printed circuit board described in above-mentioned any one of 1~4, wherein, the surface of foregoing copper foil is not
Handled with the metal beyond copper, silane coupler or bonding agent.
6. a kind of copper-clad laminated board, it possess insulating substrate and
It is laminated in aforementioned dielectric substrate surface, copper foil for printed circuit board described in above-mentioned any one of 1~5.
7. a kind of printed circuit board (PCB), it possesses the copper-clad laminated board described in above-mentioned 6.
8. according to the printed circuit board (PCB) described in above-mentioned 7, it is using semi-additive process formed with wiring pattern.
9. according to the printed circuit board (PCB) described in above-mentioned 7, it is using subtractive process formed with wiring pattern.
10. according to the printed circuit board (PCB) described in above-mentioned 8 or above-mentioned 9, wherein, the line width of foregoing wiring pattern for 20 μm with
Under.
11. a kind of manufacture method of copper foil for printed circuit board, wherein, place is etched at least one surface of copper foil
Reason so that the value of the closely sealed enhancing coefficient E shown in below general formula (1) reaches 2.5~8,
10 points of height (1) of nao-and micro relief of surface area/copper foil surface of E=copper foils
(surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of foregoing copper foil using PSTM.)
12. the manufacture method of the copper foil for printed circuit board according to above-mentioned 11, wherein, used in foregoing etching process
Fluid composition includes more than a kind in the group being made up of hydrogen peroxide, sulfuric acid, halide ion and four azoles.
13. the manufacture method of the copper foil for printed circuit board according to above-mentioned 12, wherein, foregoing etching liquid combination
Thing includes
0.2~1.5 mass % hydrogen peroxide,
0.5~3.0 mass % sulfuric acid,
0.3~3ppm halide ion and
0.01~0.3 mass % four azoles.
According to the present invention it is possible to it is good and can be by etching from exhausted to provide a kind of cementability between insulating substrate
The copper foil for printed circuit board and the printed circuit board (PCB) using the copper foil that the surface of edge base material is readily removable.
Brief description of the drawings
Fig. 1 is the 3-D view (× 30000) of the copper foil surface of embodiment 1.
Fig. 2 is the 3-D view (× 30000) of the copper foil surface of comparative example 1.
Fig. 3 is the electron microscope image (× 2000) in the wiring section of embodiment 1.
Fig. 4 is the electron microscope image (× 2000) in the wiring section of comparative example 1.
Embodiment
The printed circuit board (PCB) for being commonly used for electronic equipment etc. possesses and is laminated with the copper clad layers of copper foil on the surface of insulating substrate
Lamination.
As insulating substrate, such as epoxy resin can be made to be impregnated in the base material of glass fibre, contain phenolic resin
It is dipped in the base material of paper base material.These base materials are also sometimes referred to as prepreg.Prepreg is to instigate epoxy resin (varnish) being impregnated with
In the part that the base material semi-solid preparation that glass fibre etc. forms forms.
Electrolytic copper foil, rolled copper foil etc. can be used as copper foil.Electrolytic copper foil refers in the rotating cathode in cylinder shape
After the copper sulfate electrolyte that circulated between the anode that is configured along the rotating cathode, cupric electrolysis is set to separate out the table in rotating cathode
Face, the copper foil continuously peeled off separated out copper from rotating cathode and manufactured.On the other hand, rolled copper foil refers to passing through casting
The copper foil for carrying out calendering processing etc. obtained copper billet and manufacturing.
Surface copper foil for printed circuit board, that side is contacted with insulating substrate of the present invention is by etching and by densely
Roughening.Fluid composition (etching use fluid composition) used in etching process preferably comprise be selected from by hydrogen peroxide, sulfuric acid,
More than a kind in the group of halide ion and four azoles composition, preferably also include water.
Etching is preferably 0.2~1.5 mass % with the concentration of the hydrogen peroxide in fluid composition, more preferably 0.3~
1.2 mass %, more preferably 0.4~1.0 mass %, most preferably 0.5~0.8 mass %.The concentration quilt of hydrogen peroxide
Adjust to the etching fluid composition of this scope, the dissolution velocity of copper is big, economically excellent.
Etching is preferably 0.5~3.0 mass %, more preferably 0.5~2.5 matter with the concentration of the sulfuric acid in fluid composition
Measure %, most preferably more preferably 0.7~2.0 mass %, 1.0~1.8 mass %.The concentration of sulfuric acid is adjusted to this
The etching fluid composition of scope, the dissolution velocity of copper is big, economically excellent.
Halide ion has the effect for being roughened copper foil surface.By using the liquid group of the etching comprising halide ion
Compound is roughened copper foil surface, can improve cementability of the copper foil to insulating substrate.
As halide ion, one in the group being made up of fluorine ion, chlorion, bromide ion and iodide ion can be used
More than kind.In these, preferably chlorion or bromide ion.
Etching is preferably 0.3~3ppm with the concentration of the halide ion in fluid composition, more preferably 0.5~
2.5ppm, most preferably 0.7~2ppm.
Four azoles have the effect for being densely roughened copper foil surface by being applied in combination with halide ion.Therefore, pass through
Copper foil surface is roughened using the etching comprising four azoles with fluid composition, can further improve copper foil to insulating substrate
Cementability.
Etching is preferably selected from by 1H-TETRAZOLE, 1- methyl tetrazolium, 1- ethyls with four azoles included in fluid composition
Tetrazolium, 5- methyl tetrazolium, 5- ethyls tetrazolium, 5- Aminotetrazoles, 5- n-propyls tetrazolium, 5- mercapto-tetrazoles, 5- sulfydryl -1- methyl four
Azoles, 1,5- dimethyl tetrazolium, 1,5- diethyl tetrazolium, 1- methyl -5- ethyls tetrazolium, 1- ethyl -5- methyl tetrazolium, 1- isopropyls
More than a kind in the group of base -5- methyl tetrazolium and 1- cyclohexyl -5- methyl tetrazolium composition.More preferably be selected from by 1H-TETRAZOLE,
5- methyl tetrazolium, 5- ethyls tetrazolium, 5- sulfydryl -1- methyl tetrazolium, 1,5- dimethyl tetrazolium, 1,5- diethyl tetrazolium and 1- second
More than a kind in the group of base -5- methyl tetrazolium composition.
Etching is preferably 0.01~0.3 mass % with the concentration of four azoles in fluid composition, more preferably 0.05~
0.25 mass %, most preferably 0.1~0.2 mass %.
Using above-mentioned etching copper foil surface is etched with fluid composition.It is not particularly limited for the method for etching, can
To use the method such as known to gunite, infusion process.
The etch quantity of copper foil is preferably less than 1 μm, more preferably 0.1~1 μm, more preferably 0.2~0.9 μm, most
Preferably 0.3~0.7 μm., can be with the copper foil after being laminated insulating substrate and etching if etch quantity is within the above range
The amount of the copper foil of the embedded insulating substrate of reduction, therefore become prone to the etching in rear process and remove being somebody's turn to do in embedded insulating substrate
Copper foil.The etch quantity of copper foil refers to the value shown in below general formula (2).
Etch quantity [μm]=(quality of copper foil after quality-etching of copper foil before etching)/(etch the close of area × copper
Degree) (2)
(in formula, the density of copper is 8.96g/cm3。)
It should be noted that " etch quantity " in the present invention does not imply that each position of the copper foil by etching process
Depth, and refer to the mean depth of the copper foil surface entirety by etching process.
It is not particularly limited for the thickness of copper foil, preferably 3~35 μm, more preferably 5~30 μm.The thickness of copper foil
During in the scope, the treatability of copper foil becomes good.
It is preferred that metal, silane coupler or bonding agent beyond the unused copper in the surface that side is contacted with insulating substrate of copper foil
(priming paint) is handled.The copper foil surface of the present invention is densely roughened.Therefore, even if beyond the unused copper of copper foil of the invention
Metal, silane coupler or bonding agent etc. be surface-treated, insulating substrate can be also bonded securely.
The closely sealed enhancing coefficient E on the surface that side is contacted with insulating substrate of the copper foil for printed circuit board of present invention value
For 2.5~8.Closely sealed enhancing coefficient is preferably 2.7~7.5, more preferably 2.9~7, most preferably 3~6.5.It is if close
Close enhancing coefficient E within the above range, then can be improved close with insulating substrate formed with trickle bumps in copper foil surface
Conjunction property.Closely sealed enhancing coefficient E refers to the value shown in below general formula (1).
The point height D of nao-and micro relief ten (1) of the surface area C/ copper foil surfaces of E=copper foils
(the surface area C of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of copper foil using PSTM)
Copper foil surface area C [μm2] be equal to consider copper foil surface predetermined region in bumps when surface area divided by vacation
The value obtained by surface area during the fixed flatwise.For example, copper foil surface area C [μm2] it is equal to vertical the 5 of consideration copper foil surface
Surface area during bumps in the region that horizontal 5 μm of μ m divided by surface area (that is, 5 × 5=25) institute when assuming the flatwise
Obtained value.
The point height D of nao-and micro relief ten [μm] of copper foil surface is defined as 10 points of nao-and micro relief in JIS B 0601
Height Rzjis.The point height of nao-and micro relief ten Rzjis refers to only take sampling to grow from roughness curve along its average line direction
Degree, take the average line of part to be measured along vertical multiplying power direction from this, obtain highest crest to the absolute altitude (Yp) of the 5th high crest
Absolute value average value and the absolute value of the absolute altitude (Yv) of minimum trough to the 5th low trough average value sum, and use micron
Represent the value.
Copper foil in above-mentioned formula (1) surface area C [μm2] for consider copper foil surface bumps when surface area.Therefore,
Have that copper foil surface is more fine and close, the surface area C of copper foil becomes bigger tendency.Described " densification " refers to copper foil surface herein
The small and intensive state in convex portion one by one.
Copper foil surface area C [μm2] preferably observe copper foil surface with PSTM and obtain 3D shape number
According to value that is rear, being calculated based on the three-dimensional shape data.In addition, copper foil surface area C [μm2] it is preferably to use PSTM
The value obtained when copper foil surface is extended into 30000 times.
PSTM is the microscope for the type for detecting the tunnel current to be circulated between metal probe and sample.
By metal probes such as the sharp platinum in front end, tungsten after sample, when applying small bias between them, due to tunnel-effect
And the tunnel current that circulates.By scanning probe in a manner of the tunnel current is kept into constant, it can observe and try in atomic level
The surface configuration of sample.
The manufacture method of the copper foil for printed circuit board of the present invention is characterised by, at least one surface of copper foil is carried out
Etching process so that the value of the closely sealed enhancing coefficient E shown in below general formula (1) reaches 2.5~8,
10 points of height (1) of nao-and micro relief of surface area/copper foil surface of E=copper foils
(surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of foregoing copper foil using PSTM).Fluid composition used in etching process is such as
It is upper described.
The copper foil of the present invention is laminated in insulating substrate using method known to thermo-compression bonding etc..So obtained plywood
(copper-clad laminated board) can be used for the wiring pattern to form printed circuit board (PCB).
When the wiring pattern of printed circuit board (PCB) is formed by subtractive process, the copper foil of the present invention can be used for printed circuit board (PCB)
Conductive layer.
When the wiring pattern of printed circuit board (PCB) is formed by semi-additive process, the copper foil of the present invention can be used for printed circuit
The crystal seed layer of plate.
According to the present invention it is possible to obtain cementability between insulating substrate is good and can be by etching from insulation base
The copper foil for printed circuit board and the printed circuit board (PCB) using the copper foil that the surface of material is readily removable.
Embodiment
Embodiment 1
In embodiment 1, first prepare thickness be 12 μm, the electrolytic copper foil that size is 150mm × 150mm.Then, to institute
The glassy surface of the electrolytic copper foil of preparation is etched.The composition and etching condition of etching fluid composition are as described below.Wherein,
Glassy surface refers to the surface with cylinder shape cathode contacts side in the two sides of electrolytic copper foil.
The composition of etching fluid composition
Hydrogen peroxide：0.5 mass %
Sulfuric acid：2 mass %
1H-TETRAZOLE：0.1 mass %
Chlorion：0.5ppm
Etching condition
The temperature of etching fluid composition：30℃
Spray pressure：0.1MPa
Injecting time：1 minute
Then, with PSTM with the copper foil surface after 30000 times of multiplying power observation etching.Fig. 1 is now to see
The 3-D view of the copper foil surface measured.
Surface area after measure etching in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is
45.4[μm2].Following device is used in measure.
(SII NanoTechnology Inc. are manufactured PSTM, L-traceII/NanoNaviII
station)
Surface roughness (the Rzjis of copper foil after measure etching：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.55 [μm].Following device is used in measure.
Laser microscope (KEYENCE CORPORATION are manufactured, and VK-9700II, use 408nm violet lasers)
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 3.30.Calculating formula is such as
Shown in lower.
E={ 45.4/ (5 × 5) }/0.55=3.30
The etch quantity of copper foil surface is calculated based on above-mentioned formula (2).The result is that the etch quantity of copper foil surface is 0.5 μm.
The copper foil after etching is laminated in prepreg (Mitsubishi Gas Chemical using vacuum hotpressing machine
Company, Inc. are manufactured, trade name：HL832NS).Thus, the copper-clad laminated board being made up of prepreg and copper foil is made.At this
In copper-clad laminated board, prepreg is close on the surface for being etched side of copper foil.
Use the peel strength (Peel intensity) of so obtained copper-clad laminated board measure copper foil.Peel strength is according to JIS
The method of the defineds of C 6481 is measured.The result is that the peel strength of copper foil is 1.05kgf/cm.
Then, the surface of copper-clad laminated board is etched.The composition and etching condition of etching fluid composition are as described below.
The composition of etching fluid composition
Hydrogen peroxide：3 mass %
Sulfuric acid：7 mass %
Trade name：Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-770
Etching condition
The temperature of etching fluid composition：35℃
Spray pressure：0.2MPa
Injecting time：1 minute
Then, the copper thickness of the copper-clad laminated board after measure etching.The result is that the average thickness of 10 points of measure is 2.5
μm.Following device is used in measure.
Vortex flow copper film thickness instrument (FISCHER companies manufacture, FISCHERSCOPE MMS)
In order to form wiring pattern on copper foil, following handle is carried out.First, the copper foil of copper-clad laminated board after the etching
The upper electroless copper for implementing 0.5 μm.Then, the laminating film resist layer on the copper foil for implemented electroless copper.Then, through overexposure
Light, developing procedure, form corrosion-resisting pattern on resist layer.Then, electro-coppering is implemented to the copper foil formed with corrosion-resisting pattern.Most
Afterwards, the resist layer on copper foil is removed using resist layer stripper.Treatment conditions when removing resist layer are as described below.
Resist layer stripper
MEA：5 mass %
Trade name：Mitsubishi Gas Chemical Company, Inc. manufactures, R-100M
Treatment conditions
The temperature of resist layer stripper：50℃
Spray pressure：0.1MPa
The wiring pattern of copper foil is formed at using metallurgical microscopes (Olympus Corporation are manufactured, MX61L) measure
Size.The result is that the size of wiring pattern is line/spacing=20 μm/10 μm.
Then, crystal seed layer (copper foil) is removed from substrate using etching fluid composition.The result is that remove completely brilliant
Time required for kind layer is 1 minute.Treatment conditions when removing crystal seed layer are as described below.
The composition of etching fluid composition
Hydrogen peroxide：2 mass %
Sulfuric acid：6 mass %
Trade name：Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-800
Treatment conditions
The temperature of etching fluid composition：30℃
Spray pressure：0.2MPa
After crystal seed layer (copper foil) being removed using metallurgical microscopes (Olympus Corporation are manufactured, MX61L) measure
The Xian Kuan Minus of wiring pattern are a small amount of.The result is that Xian Kuan Minus are 5.0 μm on a small quantity.Fig. 3 is cutting for the wiring based on electron microscope
Face photo.
Embodiment 2
In example 2, by fluid composition used in the etching process of the glassy surface of electrolytic copper foil as described below
Changed, in addition, carry out experiment same as Example 1.
The composition of etching fluid composition
Hydrogen peroxide：0.5 mass %
Sulfuric acid：2 mass %
5- methyl tetrazoliums：0.1 mass %
Chlorion：1ppm
Surface area after measure etching in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is
44.7[μm2]。
Surface roughness (the Rzjis of copper foil after measure etching：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.5 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 3.58.Calculating formula is such as
It is lower described.
E={ 44.7/ (5 × 5) }/0.5=3.58
The etch quantity of copper foil surface is calculated based on above-mentioned formula (2).The result is that the etch quantity of copper foil surface is 0.4 μm.
The peel strength of copper foil is 1.00kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 5.0 μm on a small quantity.
Embodiment 3
In embodiment 3, by fluid composition used in the etching process of the glassy surface of electrolytic copper foil as described below
Changed, in addition, carry out experiment same as Example 1.
The composition of etching fluid composition
Hydrogen peroxide：1 mass %
Sulfuric acid：2.5 mass %
5- methyl tetrazoliums：0.05 mass %
1,5- dimethyl tetrazoliums：0.05 mass %
Chlorion：1ppm
Surface area after measure etching in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is
38[μm2]。
Surface roughness (the Rzjis of copper foil after measure etching：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.25 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 6.08.Calculating formula is such as
It is lower described.
E={ 38/ (5 × 5) }/0.25=6.08
The etch quantity of copper foil surface is calculated based on above-mentioned formula (2).The result is that the etch quantity of copper foil surface is 0.3 μm.
The peel strength of copper foil is 0.9kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 4.5 μm on a small quantity.
Embodiment 4
In example 4, the etching condition of the etching process of the glassy surface of electrolytic copper foil is changed as described below,
In addition, experiment same as Example 3 is carried out.
Etching condition
The temperature of etching fluid composition：35℃
Spray pressure：0.2MPa
Injecting time：1 minute
Surface area after measure etching in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is
45[μm2]。
Surface roughness (the Rzjis of copper foil after measure etching：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.45 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 4.0.Calculating formula is such as
It is lower described.
E={ 45/ (5 × 5) }/0.45=4.0
The etch quantity of copper foil surface is calculated based on above-mentioned formula (2).The result is that the etch quantity of copper foil surface is 0.65 μm.
The peel strength of copper foil is 0.95kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 5.0 μm on a small quantity.
Comparative example 1
In comparative example 1, the following electrolytic copper foil that is roughened in advance using a surface, in addition, carry out with it is real
Apply the experiment of the identical of example 1.
Electrolytic copper foil
Thickness：12μm
Trade name：MITSUI MINING＆SMELTING CO., LTD. manufactures, 3EC-VLP
The surface of above-mentioned electrolytic copper foil is observed with 30000 times of multiplying power using PSTM.Fig. 2 is now to observe
The 3-D view of the copper foil surface arrived.
Determine the surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is 36.2 [μ
m2]。
Determine the surface roughness (Rzjis of copper foil：10 points of height of nao-and micro relief).The result is that the rough surface of copper foil
Spend for 3.65 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 0.40.Calculating formula is such as
It is lower described.
E={ 36.2/ (5 × 5) }/3.65=0.40
The peel strength of copper foil is 0.90kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 9.8 μm on a small quantity.Fig. 4 is the wiring based on electron microscope
Cross-section photograph.
Comparative example 2
In comparative example 2, the following electrolytic copper foil that is roughened in advance using a surface, in addition, carry out with it is real
Apply the experiment of the identical of example 1.
Electrolytic copper foil
Thickness：12μm
Trade name：FURUKAWA ELECTRIC CO., LTD. manufactures, FV-WS
Determine the surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is 33.8 [μ
m2]。
Determine the surface roughness (Rzjis of copper foil：10 points of height of nao-and micro relief).The result is that the rough surface of copper foil
Spend for 2.20 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 0.61.Calculating formula is such as
It is lower described.
E={ 33.8/ (5 × 5) }/2.20=0.61
The peel strength of copper foil is 0.85kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 9.5 μm on a small quantity.
Comparative example 3
In comparative example 3, the following electrolytic copper foil that is roughened in advance using a surface, in addition, carry out with it is real
Apply the experiment of the identical of example 1.
Electrolytic copper foil
Thickness：12μm
Trade name：JX Nippon Mining＆Metals Corporation are manufactured, HLPLC
Determine the surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is 32.2 [μ
m2]。
Determine the surface roughness (Rzjis of copper foil：10 points of height of nao-and micro relief).The result is that the rough surface of copper foil
Spend for 2.05 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 0.63.Calculating formula is such as
It is lower described.
E={ 32.2/ (5 × 5) }/2.05=0.63
The peel strength of copper foil is 0.85kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 9.3 μm on a small quantity.
Comparative example 4
In comparative example 4, the following electrolytic copper foil that is roughened in advance using a surface, in addition, carry out with it is real
Apply the experiment of the identical of example 1.
Electrolytic copper foil
Thickness：12μm
Trade name：FUKUDA METAL FOIL＆POWDER Co., LTD. manufactures, SV
Determine the surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface.The result is that the surface area of copper foil is 31.3 [μ
m2]。
Determine the surface roughness (Rzjis of copper foil：10 points of height of nao-and micro relief).The result is that the rough surface of copper foil
Spend for 1.85 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 0.68.Calculating formula is such as
It is lower described.
E={ 31.3/ (5 × 5) }/1.85=0.68
The peel strength of copper foil is 0.70kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 9.0 μm on a small quantity.
Comparative example 5
In comparative example 5, by fluid composition used in the etching process of the glassy surface of electrolytic copper foil as described below
Changed, in addition, carry out experiment same as Example 1.
The composition of etching fluid composition
Hydrogen peroxide：1.3 mass %
Sulfuric acid：5 mass %
5- Aminotetrazoles：0.35 mass %
Trade name：Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-900
Surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface after measure etching.The result is that the surface area of copper foil
For 36 [μm2]。
Surface roughness (the Rzjis of copper foil after measure etching：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.75 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 1.92.Calculating formula is such as
It is lower described.
E={ 36/ (5 × 5) }/0.75=1.92
The etch quantity of copper foil surface is calculated based on above-mentioned formula (2).The result is that the etch quantity of copper foil surface is 1.5 μm.
The peel strength of copper foil is 0.50kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 6.5 μm on a small quantity.
Comparative example 6
In comparative example 6, in addition to not etching the glassy surface of electrolytic copper foil, experiment same as Example 1 is carried out.
Surface area in the horizontal 5 μm of regions of vertical 5 μ ms of copper foil surface (untreated) for 25 [μm2]。
Determine the surface roughness (Rzjis of copper foil (untreated)：10 points of height of nao-and micro relief).The result is that copper foil
Surface roughness is 0.1 [μm].
Closely sealed enhancing coefficient E is calculated based on above-mentioned formula (1).The result is that closely sealed enhancing coefficient E is 10.Calculating formula is as follows
It is described.
E={ 25/ (5 × 5) }/0.1=10
The peel strength of copper foil is 0.20kgf/cm.
The Xian Kuan Minus for removing the wiring pattern after crystal seed layer are 4.5 μm on a small quantity.
The result of embodiment 1~4 and comparative example 1~6 is shown in table 1 below.
[table 1]
The closely sealed enhancing coefficient E compared with comparative example 1~5 of embodiment 1~4 is big.
The peel strength of copper foil compared with comparative example 1~6 of embodiment 1,2 and 4 is big.
Embodiment 3 is equal with the peel strength of comparative example 1, and the peel strength of copper foil is big compared with comparative example 2~6.
The Xian Kuan Minus of wiring pattern compared with comparative example 1~5 of embodiment 1~4 are small on a small quantity.
The etch quantity compared with comparative example 5 of embodiment 1~4 is few.
Adaptation between the copper foil and insulating substrate of the present invention is good.
The Xian Kuan Minus of the wiring pattern of the copper foil of the present invention are small on a small quantity, therefore can form trickle wiring pattern.
The printed circuit board (PCB) that the line width that the copper foil of the present invention can be used for wiring pattern well is less than 20 μm.
Claims (10)
1. a kind of copper foil for printed circuit board, wherein, the closely sealed enhancing coefficient E shown in the below general formula (1) at least one surface
Value be 2.5~8,
10 points of height ... (1) of nao-and micro relief of surface area/copper foil surface of E=copper foils
Wherein, the surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of the copper foil using PSTM,
Wherein, the surface of the copper foil is etched processing,
Fluid composition used in the etching process, which includes, to be selected from by hydrogen peroxide, sulfuric acid, halide ion and four azole groups
Into group in more than a kind.
2. copper foil for printed circuit board according to claim 1, wherein, the copper foil surface shown in below general formula (2)
Etch quantity be less than 1 μm,
Etch quantity [μm]=(quality of copper foil after quality-etching of copper foil before etching)/(density of etching area × copper) ... (2)
In formula, the density of copper is 8.96g/cm3。
3. copper foil for printed circuit board according to claim 1 or 2, wherein, beyond the unused copper in surface of the copper foil
Metal, silane coupler or bonding agent are handled.
4. a kind of copper-clad laminated board, it possess insulating substrate and
It is laminated in the copper foil for printed circuit board described in any one of described insulating substrate surface, claims 1 to 3.
5. a kind of printed circuit board (PCB), it possesses the copper-clad laminated board described in claim 4.
6. printed circuit board (PCB) according to claim 5, it is using semi-additive process formed with wiring pattern.
7. printed circuit board (PCB) according to claim 5, it is using subtractive process formed with wiring pattern.
8. the printed circuit board (PCB) according to claim 6 or 7, wherein, the line width of the wiring pattern is less than 20 μm.
9. a kind of manufacture method of copper foil for printed circuit board, wherein, at least one surface of copper foil is etched, made
The value for obtaining the closely sealed enhancing coefficient E shown in below general formula (1) reaches 2.5~8,
10 points of height (1) of nao-and micro relief of surface area/copper foil surface of E=copper foils
Wherein, the surface area of copper foil is the average surface area of the horizontal 1 μm unit area of vertical 1 μ m of copper foil, the surface area of copper foil
To observe the value obtained during the surface of the copper foil using PSTM,
Wherein, the fluid composition used in the etching process, which includes, is selected from by hydrogen peroxide, sulfuric acid, halide ion and tetrazolium
More than a kind in the group of class composition.
10. the manufacture method of copper foil for printed circuit board according to claim 9, wherein, used in the etching process
Fluid composition includes
0.2~1.5 mass % hydrogen peroxide,
0.5~3.0 mass % sulfuric acid,
0.3~3ppm halide ion and
0.01~0.3 mass % four azoles.
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| JP2012-128737 | 2012-06-06 | ||
| JP2013-091688 | 2013-04-24 | ||
| JP2013091688A JP6225467B2 (en) | 2012-06-06 | 2013-04-24 | Copper foil for printed wiring board, method for producing the same, and printed wiring board using the copper foil |
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| JP7310753B2 (en) | 2020-08-20 | 2023-07-19 | 新東工業株式会社 | Joint strength estimation method and joint strength estimation device |
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| US5482784A (en) * | 1993-12-24 | 1996-01-09 | Mitsui Mining And Smelting Co., Ltd. | Printed circuit inner-layer copper foil and process for producing the same |
| JP3476264B2 (en) | 1993-12-24 | 2003-12-10 | 三井金属鉱業株式会社 | Copper foil for printed circuit inner layer and method of manufacturing the same |
| JP3881419B2 (en) | 1997-03-27 | 2007-02-14 | 日鉱金属株式会社 | Copper or copper alloy material with excellent resin adhesion |
| JP4687852B2 (en) * | 2001-06-25 | 2011-05-25 | 三菱瓦斯化学株式会社 | Surface treatment agent for copper and copper alloys |
| JP2004263300A (en) | 2003-02-12 | 2004-09-24 | Furukawa Techno Research Kk | Copper foil for fine pattern printed circuit and manufacturing method therefor |
| US20050067378A1 (en) * | 2003-09-30 | 2005-03-31 | Harry Fuerhaupter | Method for micro-roughening treatment of copper and mixed-metal circuitry |
| JP4567360B2 (en) * | 2004-04-02 | 2010-10-20 | 三井金属鉱業株式会社 | Copper foil manufacturing method and copper foil obtained by the manufacturing method |
| JP2005292057A (en) * | 2004-04-02 | 2005-10-20 | Mitsui Mining & Smelting Co Ltd | Method for evaluating adhesive strength of roughened surface of copper foil |
| JP2006210689A (en) | 2005-01-28 | 2006-08-10 | Fukuda Metal Foil & Powder Co Ltd | Copper foil for high frequency printed wiring board and its production method |
| JP5215631B2 (en) * | 2007-10-24 | 2013-06-19 | 三井金属鉱業株式会社 | Surface treated copper foil |
| JP5181618B2 (en) * | 2007-10-24 | 2013-04-10 | 宇部興産株式会社 | Metal foil laminated polyimide resin substrate |
| JP5400447B2 (en) | 2009-03-31 | 2014-01-29 | 三井金属鉱業株式会社 | Roughened copper foil, method for producing roughened copper foil, and copper-clad laminate |
| JP2011038124A (en) * | 2009-08-06 | 2011-02-24 | Mitsubishi Gas Chemical Co Inc | Metal surface treatment agent |
| JP4927963B2 (en) * | 2010-01-22 | 2012-05-09 | 古河電気工業株式会社 | Surface-treated copper foil, method for producing the same, and copper-clad laminate |
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