CN103476198A - Copper foil for printed wiring board, process for preparing the same, and printed wiring board using the copper foil - Google Patents
Copper foil for printed wiring board, process for preparing the same, and printed wiring board using the copper foil Download PDFInfo
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- CN103476198A CN103476198A CN2013102239525A CN201310223952A CN103476198A CN 103476198 A CN103476198 A CN 103476198A CN 2013102239525 A CN2013102239525 A CN 2013102239525A CN 201310223952 A CN201310223952 A CN 201310223952A CN 103476198 A CN103476198 A CN 103476198A
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- copper foil
- printed circuit
- circuit board
- surface area
- copper
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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
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—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 copper foil for a printed wiring board, a process for preparing the same, and the printed wiring board using the copper foil. The coper foil for the printed wiring board has high adhesion with an insulating substrate, and furthermore can be easily eliminated from the surface of insulating substrate through etching. The value of an adhesion reinforcement coefficient E represented by a general formula (1) of at least one surface of the printed wiring board of the invention is 2.5-8, E=(surface area of the copper foil)/(ten point heights of microscopic roughness on the surface of the copper foil) (1); wherein, the surface area of the copper foil is an average surface area of a unit area with a size of 1 mu m*1 mu m on the copper foil, and the surface area of the copper foil is a value which is obtained when the surface of the copper foil is observed through a scanning tunnel microscope.
Description
Related application
The application follows to take the application of Japanese patent application 2012-128737 as the claim of priority of basic Paris Convention.Therefore, the application comprises the disclosed whole items of this Japanese patent application.
Technical field
The present invention relates to copper foil for printed circuit board, more specifically, relate to for copper foil for printed circuit board and the manufacture method thereof of electronic equipment etc. and the printed circuit board (PCB) that uses this Copper Foil.
Background technology
In recent years, along with miniaturization, lightweight and the high performance of electronic equipment, the becoming more meticulous of tight demand printed circuit board wiring pattern.Printed circuit board (PCB) is used to such as semiconductor mounting substrate, motherboard substrate etc.
At present, as the method that forms the copper wiring case on printed circuit board (PCB), known have subtractive process and a semi-additive process.
In subtractive process, at first in the surperficial laminated copper foil of insulating substrate.Then, at copper foil surface, form resist layer, on this resist layer, utilize photoetching process to form pattern.Then, the part do not covered with resist layer of Copper Foil is removed in etching, forms thus the copper wiring case.
In semi-additive process, at first on the surface of insulating substrate, form the thin metal layer that is called as crystal seed layer.Then, on the crystal seed layer surface, form resist layer, by photoetching process, on this resist layer, form pattern.Then, implement electro-coppering by the part do not covered with resist layer to crystal seed layer and form the copper wiring case.The copper-plated part of not enforcement of crystal seed layer is removed by etching.
In semi-additive process, when crystal seed layer utilizes electrolytic copper foil or rolled copper foil to form, implement roughening on a surface of Copper Foil (contacting the surface of a side with insulating substrate) and process.If the surface of Copper Foil is roughened, on the surface of Copper Foil, form trickle protuberance.By making this protuberance stretch into the inside of insulating substrate, can bring into play the anchoring effect of physical property, make the Copper Foil strong bond in the surface of insulating substrate.
But, have following problem in existing printed circuit board (PCB).In semi-additive process, when the roughening degree of copper foil surface is large, the protuberance of copper foil surface excessively gos deep into the inside of insulating substrate.In this case, elongated from the needed etching period of surface removal Copper Foil (crystal seed layer) of insulating substrate.In addition, the elongated result of etching period is that the minimizing quantitative change of live width of copper wiring case is large, therefore becomes and is difficult to form trickle copper wiring case.
On the other hand, when the roughening degree on Copper Foil (crystal seed layer) surface is too small, the cementability variation between Copper Foil and insulating substrate, so Copper Foil becomes and is easy to the sur-face peeling from insulating substrate, becomes and is difficult to form trickle copper wiring case.
As the prior art of the surface roughness about Copper Foil, known have a following technology.In Japanese kokai publication hei 07-231152 communique (patent documentation 1), the Copper Foil that a kind of surface roughness is 1～3 μ m is disclosed.It is the trickle pimple of anti-teardrop shaped that 0.6～1.0 μ m, maximum gauge are 0.2～0.8 μ m that the surface of this Copper Foil is provided with length.In TOHKEMY 2006-210689 communique (patent documentation 2), a kind of Copper Foil is disclosed, the surface roughness of described Copper Foil (Rz: be 10 height of nao-and micro relief) below 2.5 μ m, the roughening processing layer that the spheroidal particle that to have by diameter be 0.05～1.0 μ m forms, have by the antirust coat formed more than at least one of Mo, Ni, W, P, Co, Ge and have silane coupled layer on this roughening processing layer.In TOHKEMY 2004-263300 communique (patent documentation 3), a kind of Copper Foil is disclosed, the surface roughness of described Copper Foil (Rz) is below 2.5 μ m, the minimum peak spacing at matrix peak is more than 5 μ m, and it is the following crystal grains of 2 μ m that there is average grain diameter in surface.In TOHKEMY 2010-236058 communique (patent documentation 4), a kind of Copper Foil that comprises the trickle copper particle that the angle θ of crown section is the following overshooting shape of 85 degree is disclosed.In Japanese kokai publication hei 10-265872 communique (patent documentation 5), a kind of copper or Cu alloy material are disclosed, the arithmetic average roughness of electron beam three-dimensional roughness resolver based on being extended to the surface of 1000 times that utilize of described material is 0.05～0.8 μ m, and surface area replacement value is 1.005～1.08.
Summary of the invention
Yet the discoveries such as the inventor are when in patent documentation 1～5, disclosed Copper Foil is adhered to insulating substrate, the protuberance of copper foil surface excessively gos deep into the inside of insulating substrate, therefore removes the needed etching period of Copper Foil elongated.Its result, the minimizing quantitative change of copper wiring case live width is large, therefore becomes and is difficult to form trickle copper wiring case.
The object of the present invention is to provide cementability between a kind of and insulating substrate good and the copper foil for printed circuit board that can easily remove from the surface of insulating substrate by etching and the printed circuit board (PCB) that uses this Copper Foil.
The present invention is as described below.
1. a copper foil for printed circuit board, wherein, the value of the closely sealed enhancing coefficient E shown in the following general formula (1) at least one surface is 2.5～8,
10 height of the nao-and micro relief of the surface area/copper foil surface of E=Copper Foil ... (1)
(average surface area of the unit area of the surface area of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope to observe described Copper Foil surperficial.)
2. according to above-mentioned 1 described copper foil for printed circuit board, wherein, the etched processing in the surface of aforementioned Copper Foil.
3. according to above-mentioned 2 described copper foil for printed circuit board, wherein, the etch quantity of the aforementioned copper foil surface shown in following general formula (2) is below 1 μ m,
Etch quantity [μ m]=(quality of Copper Foil after the quality-etching of the front Copper Foil of etching)/(density of etching area * copper) ... (2)
(in formula, the density of copper is 8.96g/cm
3.)
4. according to above-mentioned 2 or 3 described copper foil for printed circuit board, wherein, aforementioned etch processes fluid composition used comprise in the group of selecting free hydrogen peroxide, sulfuric acid, halide ion and tetrazolium class to form more than a kind.
5. according to the described copper foil for printed circuit board of any one in above-mentioned 1～4, wherein, the surface of aforementioned Copper Foil is not processed with metal, silane coupler or bonding agent beyond copper.
6. a copper-clad laminated board, it possess insulating substrate and
Be laminated in the described copper foil for printed circuit board of any one aforementioned dielectric substrate surface, in above-mentioned 1～5.
7. a printed circuit board (PCB), it possesses above-mentioned 6 described copper-clad laminated boards.
8. according to above-mentioned 7 described printed circuit board (PCB)s, it utilizes semi-additive process to be formed with wiring pattern.
9. according to above-mentioned 7 described printed circuit board (PCB)s, it utilizes subtractive process to be formed with wiring pattern.
10. according to above-mentioned 8 or above-mentioned 9 described printed circuit board (PCB)s, wherein, the live width of aforementioned wiring pattern is below 20 μ m.
11. the manufacture method of a copper foil for printed circuit board, wherein, carry out etch processes at least one surface of Copper Foil, makes the value of the closely sealed enhancing coefficient E shown in following general formula (1) reach 2.5～8,
10 height of the nao-and micro relief of the surface area/copper foil surface of E=Copper Foil ... (1)
(average surface area of the unit area of the surface area of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope to observe aforementioned Copper Foil surperficial.)
12. according to the manufacture method of above-mentioned 11 described copper foil for printed circuit board, wherein, aforementioned etch processes fluid composition used comprise in the group of selecting free hydrogen peroxide, sulfuric acid, halide ion and tetrazolium class to form more than a kind.
13., according to the manufacture method of above-mentioned 12 described copper foil for printed circuit board, wherein, aforementioned etching comprises with fluid composition
0.2 the hydrogen peroxide of～1.5 quality %,
0.5 the sulfuric acid of～3.0 quality %,
0.3 the halide ion of～3ppm and
0.01 the tetrazolium class of～0.3 quality %.
According to the present invention, can provide cementability between a kind of and insulating substrate good and the copper foil for printed circuit board that can easily remove from the surface of insulating substrate by etching and the printed circuit board (PCB) that uses this Copper Foil.
The accompanying drawing explanation
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 cross section of embodiment 1.
Fig. 4 is the electron microscope image (* 2000) in the wiring cross section of comparative example 1.
Embodiment
Usually, the printed circuit board (PCB) for electronic equipment etc. possesses the copper-clad laminated board that is laminated with Copper Foil on the surface of insulating substrate.
As insulating substrate, for example can use epoxy resin be impregnated in glass fibre base material, make phenolic resins be impregnated 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) is impregnated in to the parts that base material semi-solid preparation that glass fibre etc. forms forms.
Can use electrolytic copper foil, rolled copper foil etc. as Copper Foil.Electrolytic copper foil refers at the rotating cathode that is the cylinder shape and after circulation copper sulfate electrolyte between the anode of this rotating cathode configuration, makes cupric electrolysis separate out the surface in rotating cathode, peels off separated out copper and the Copper Foil manufactured from rotating cathode continuously.On the other hand, rolled copper foil refers to wait copper billet obtained to roll the Copper Foil that processing is manufactured by casting.
Surface copper foil for printed circuit board of the present invention, contact a side with insulating substrate by etching by roughening densely.Etch processes fluid composition (etching fluid composition) used preferably comprise in the group of selecting free hydrogen peroxide, sulfuric acid, halide ion and tetrazolium class to form more than a kind, preferably also comprise water.
Etching is preferably 0.2～1.5 quality % by the concentration of the hydrogen peroxide in fluid composition, 0.3～1.2 quality % more preferably, and more preferably 0.4～1.0 quality %, most preferably be 0.5～0.8 quality %.The concentration of hydrogen peroxide is adjusted to the etching fluid composition of this scope, and the dissolution velocity of copper is large, excellent economically.
Etching is preferably 0.5～3.0 quality % by the concentration of the sulfuric acid in fluid composition, 0.5～2.5 quality % more preferably, and more preferably 0.7～2.0 quality %, most preferably be 1.0～1.8 quality %.The concentration of sulfuric acid is adjusted to the etching fluid composition of this scope, and the dissolution velocity of copper is large, excellent economically.
Halide ion has the effect that makes the copper foil surface roughening.The etching that comprises halide ion by use carrys out the roughening copper foil surface with fluid composition, can improve the cementability of Copper Foil to insulating substrate.
As halide ion, can use more than one in the group of selecting free fluorine ion, chloride ion, bromide ion and iodide ion to form.In these, preferably chloride ion or bromide ion.
Etching is preferably 0.3～3ppm by the concentration of the halide ion in fluid composition, and more preferably 0.5～2.5ppm, most preferably be 0.7～2ppm.
The tetrazolium class, by being used in combination with halide ion, has the effect of roughening copper foil surface densely.Therefore, the etching that comprises the tetrazolium class by use carrys out the roughening copper foil surface with fluid composition, can further improve the cementability of Copper Foil to insulating substrate.
Etching is preferably and selects free 1H-TETRAZOLE, 1-methyl tetrazolium, 1-ethyl tetrazolium, 5-methyl tetrazolium, 5-ethyl tetrazolium, 5-Aminotetrazole, 5-n-pro-pyl tetrazolium, 5-mercapto-tetrazole, 5-sulfydryl-1-methyl tetrazolium, 1 by the tetrazolium class comprised in fluid composition, 5-dimethyl tetrazolium, 1, in the group that 5-diethyl tetrazolium, 1-methyl-5-ethyl tetrazolium, 1-ethyl-5-methyl tetrazolium, 1-isopropyl-5-methyl tetrazolium and 1-cyclohexyl-5-methyl tetrazolium form more than a kind.More preferably select free 1H-TETRAZOLE, 5-methyl tetrazolium, 5-ethyl tetrazolium, 5-sulfydryl-1-methyl tetrazolium, 1,5-dimethyl tetrazolium, 1, in the group that 5-diethyl tetrazolium and 1-ethyl-5-methyl tetrazolium form more than a kind.
Etching is preferably 0.01～0.3 quality % by the concentration of the tetrazolium class in fluid composition, and more preferably 0.05～0.25 quality %, most preferably be 0.1～0.2 quality %.
Use fluid composition etching copper foil surface for above-mentioned etching.Be not particularly limited for etching method, can use known methods such as gunite, infusion process.
The etch quantity of Copper Foil is preferably below 1 μ m, 0.1～1 μ m more preferably, and more preferably 0.2～0.9 μ m, most preferably be 0.3～0.7 μ m.If etch quantity, in above-mentioned scope, can reduce the amount of this Copper Foil that embeds insulating substrate during the Copper Foil after stacked insulating substrate and etching, therefore becoming is easy to etching in rear operation and removes this Copper Foil embedded in insulating substrate.The etch quantity of Copper Foil refers to the value shown in following general formula (2).
Etch quantity [μ m]=(quality of Copper Foil after the quality-etching of the front Copper Foil of etching)/(density of etching area * copper) ... (2)
(in formula, the density of copper is 8.96g/cm
3.)
It should be noted that, " etch quantity " in the present invention do not refer to the degree of depth through each position of the Copper Foil of etch processes, and refers to the mean depth through the copper foil surface integral body of etch processes.
Thickness for Copper Foil is not particularly limited, and is preferably 3～35 μ m, more preferably 5～30 μ m.The thickness of Copper Foil is when this scope, and it is good that the treatability of Copper Foil becomes.
Preferably the surface that contacts a side with insulating substrate of Copper Foil is not processed with metal, silane coupler or bonding agent (priming paint) beyond copper.Copper foil surface of the present invention is by roughening densely.Therefore, even Copper Foil of the present invention does not carry out surface treatment with metal, silane coupler or bonding agent etc. beyond copper, also can be bonding securely to insulating substrate.
The value of the closely sealed enhancing coefficient E on the surface that contacts a side with insulating substrate of copper foil for printed circuit board of the present invention is 2.5～8.Closely sealed enhancing coefficient is preferably 2.7～7.5, and more preferably 2.9～7, most preferably be 3～6.5.If it is trickle concavo-convex that closely sealed enhancing coefficient E, in above-mentioned scope, is formed with at copper foil surface, can improve the adaptation with insulating substrate.Closely sealed enhancing coefficient E refers to the value shown in following general formula (1).
10 height D of the nao-and micro relief of the surface area C/ copper foil surface of E=Copper Foil ... (1)
(average surface area of the unit area of the surface area C of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope observation Copper Foil surperficial)
The surface area C[μ m of Copper Foil
2] surface area while equaling to consider concavo-convex in the regulation zone of the copper foil surface resulting value of surface area when smooth divided by this zone of supposition.For example, the surface area C[μ m of Copper Foil
2] surface area when supposing that this zone is smooth of surface area while equaling to consider concavo-convex in the zone of the vertical 5 μ m of copper foil surface * horizontal 5 μ m (, 5 * 5=25) and resulting value.
10 of the nao-and micro reliefs of copper foil surface height D[μ m] be defined as 10 height Rzjis of nao-and micro relief in JIS B0601.10 height Rzjis of nao-and micro relief refer to from roughness curve and only take sample length along its average line direction, from this, take the average line of part to be measured along vertical multiplying power direction, obtain the mean value sum of absolute value of the absolute altitude (Yv) of the mean value of absolute value of absolute altitude (Yp) of the highest crest to the 5 high crests and minimum trough to the 5 low troughs, and with micron meaning this value.
The surface area C[μ m of the Copper Foil in above-mentioned general formula (1)
2] surface area when considering copper foil surface concavo-convex.Therefore, the tendency that exists the surface area C of the finer and close Copper Foil of copper foil surface to become larger.Herein said " densification " refer to the small and intensive state of protuberance one by one of copper foil surface.
The surface area C[μ m of Copper Foil
2] be preferably with scanning tunnel microscope observation copper foil surface and after obtaining three-dimensional shape data, the value of calculating based on this three-dimensional shape data.In addition, the surface area C[μ m of Copper Foil
2] be preferably while by scanning tunnel microscope, copper foil surface being extended to 30000 times the value obtained.
Scanning tunnel microscope is to detect the microscope of the type of the tunnel current circulated between metal probe and sample.By front end, the metal probes such as sharp-pointed platinum, tungsten are near after sample, while applying small bias voltage between them, due to the tunnel effect tunnel current that circulates.By this tunnel current is kept to constant mode scan-probe, can observe at atomic level the surface configuration of sample.
The manufacture method of copper foil for printed circuit board of the present invention is characterised in that, etch processes is carried out at least one surface of Copper Foil, makes the value of the closely sealed enhancing coefficient E shown in following general formula (1) reach 2.5～8,
10 height of the nao-and micro relief of the surface area/copper foil surface of E=Copper Foil ... (1)
(average surface area of the unit area of the surface area of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope to observe aforementioned Copper Foil surperficial).Etch processes fluid composition used as mentioned above.
The known methods such as use thermo-compressed are laminated in insulating substrate by Copper Foil of the present invention.The plywood so obtained (copper-clad laminated board) can be used to form the wiring pattern of printed circuit board (PCB).
When the wiring pattern of printed circuit board (PCB) forms by subtractive process, Copper Foil of the present invention can be used for to the conductive layer of printed circuit board (PCB).
When the wiring pattern of printed circuit board (PCB) forms by semi-additive process, Copper Foil of the present invention can be used for to the crystal seed layer of printed circuit board (PCB).
According to the present invention, can obtain and insulating substrate between cementability good and the copper foil for printed circuit board that can easily remove from the surface of insulating substrate by etching and the printed circuit board (PCB) that uses this Copper Foil.
Embodiment
embodiment 1
In embodiment 1, at first to prepare thickness be 12 μ m, be of a size of the electrolytic copper foil of 150mm * 150mm.Then, the glassy surface of prepared electrolytic copper foil carried out to etching.Etching is as described below with composition and the etching condition of fluid composition.Wherein, glassy surface refers to the surface that contacts a side in the two sides of electrolytic copper foil with cylinder shape negative electrode.
The composition of fluid composition for etching
Hydrogen peroxide: 0.5 quality %
Sulfuric acid: 2 quality %
1H-TETRAZOLE: 0.1 quality %
Chloride ion: 0.5ppm
Etching condition
The temperature of fluid composition for etching: 30 ℃
Expulsion pressure: 0.1MPa
Injecting time: 1 minute
Then, the copper foil surface after with the multiplying power of 30000 times observation etching by scanning tunnel microscope.Fig. 1 is the 3-D view of the copper foil surface that now observes.
Surface area after the mensuration etching in the vertical 5 μ m of copper foil surface * horizontal 5 μ m zones.Consequently the surface area of Copper Foil is 45.4[μ m
2].In mensuration, use with lower device.
Scanning tunnel microscope (SII NanoTechnology Inc. manufactures, L-traceII/NanoNaviII station)
Surface roughness (the Rzjis: 10 height of nao-and micro relief) of the Copper Foil after the mensuration etching.Consequently the surface roughness of Copper Foil is 0.55[μ m].In mensuration, use with lower device.
Laser microscope (KEYENCE CORPORATION manufactures, VK-9700II, use 408nm violet laser)
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 3.30.Calculating formula is as follows.
E={45.4/(5×5)}/0.55=3.30
Calculate the etch quantity of copper foil surface based on above-mentioned general formula (2).Consequently the etch quantity of copper foil surface is 0.5 μ m.
(Mitsubishi Gas Chemical Company, Inc. manufactures, trade name: HL832NS) to utilize vacuum hotpressing machine that the Copper Foil after etching is laminated in to prepreg.Thus, make the copper-clad laminated board formed by prepreg and Copper Foil.In this copper-clad laminated board, prepreg is close on the surface of an etched side of Copper Foil.
Use the copper-clad laminated board so obtained to measure the peel strength (Peel intensity) of Copper Foil.Peel strength is measured according to the method for JIS C6481 defined.Consequently the peel strength of Copper Foil is 1.05kgf/cm.
Then, the surface of etching copper-clad laminated board.Etching is as described below with composition and the etching condition of fluid composition.
The composition of fluid composition for etching
Hydrogen peroxide: 3 quality %
Sulfuric acid: 7 quality %
Trade name: Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-770
Etching condition
The temperature of fluid composition for etching: 35 ℃
Expulsion pressure: 0.2MPa
Injecting time: 1 minute
Then, the copper thickness of the copper-clad laminated board after the mensuration etching.The average thickness of consequently measuring at 10 is 2.5 μ m.In mensuration, use with lower device.
Vortex flow copper film thickness gauge (FISCHER company manufactures, FISCHERSCOPE MMS)
In order to form wiring pattern on Copper Foil, carry out following processing.At first, implement the electroless copper of 0.5 μ m on the Copper Foil of the copper-clad laminated board after etching.Then, implementing laminating film resist layer on the Copper Foil of electroless copper.Then, through overexposure, developing procedure, form corrosion-resisting pattern on resist layer.Then, the Copper Foil that is formed with corrosion-resisting pattern is implemented to electro-coppering.Finally, use the resist layer stripper to remove the resist layer on Copper Foil.Treatment conditions while removing resist layer are as described below.
The resist layer stripper
Monoethanolamine: 5 quality %
Trade name: Mitsubishi Gas Chemical Company, Inc. manufactures, R-100M
Treatment conditions
The temperature of resist layer stripper: 50 ℃
Expulsion pressure: 0.1MPa
(Olympus Corporation manufactures, and MX61L) measures the size of the wiring pattern that is formed at Copper Foil to use metallurgical microscopes.Consequently wiring pattern is of a size of line/spacing=20 μ m/10 μ m.
Then, use etching to remove crystal seed layer (Copper Foil) with fluid composition from substrate.Consequently removing the needed time of crystal seed layer fully is 1 minute.Treatment conditions while removing crystal seed layer are as described below.
The composition of fluid composition for etching
Hydrogen peroxide: 2 quality %
Sulfuric acid: 6 quality %
Trade name: Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-800
Treatment conditions
The temperature of fluid composition for etching: 30 ℃
Expulsion pressure: 0.2MPa
(Olympus Corporation manufactures, and MX61L) the Xian Kuan Minus of the wiring pattern after mensuration removal crystal seed layer (Copper Foil) is a small amount of to use metallurgical microscopes.Consequently Xian Kuan Minus is 5.0 μ m on a small quantity.Fig. 3 is based on the cross-section photograph of the wiring of electron microscope.
embodiment 2
In embodiment 2, fluid composition used in the etch processes of the glassy surface of electrolytic copper foil is changed as described below, in addition, carry out the test identical with embodiment 1.
The composition of fluid composition for etching
Hydrogen peroxide: 0.5 quality %
Sulfuric acid: 2 quality %
5-methyl tetrazolium: 0.1 quality %
Chloride ion: 1ppm
Surface area after the mensuration etching in the vertical 5 μ m of copper foil surface * horizontal 5 μ m zones.Consequently the surface area of Copper Foil is 44.7[μ m
2].
Surface roughness (the Rzjis: 10 height of nao-and micro relief) of the Copper Foil after the mensuration etching.Consequently the surface roughness of Copper Foil is 0.5[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 3.58.Calculating formula is as described below.
E={44.7/(5×5)}/0.5=3.58
Calculate the etch quantity of copper foil surface based on above-mentioned general formula (2).Consequently the etch quantity of copper foil surface is 0.4 μ m.
The peel strength of Copper Foil is 1.00kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 5.0 μ m on a small quantity.
embodiment 3
In embodiment 3, fluid composition used in the etch processes of the glassy surface of electrolytic copper foil is changed as described below, in addition, carry out the test identical with embodiment 1.
The composition of fluid composition for etching
Hydrogen peroxide: 1 quality %
Sulfuric acid: 2.5 quality %
5-methyl tetrazolium: 0.05 quality %
1,5-dimethyl tetrazolium: 0.05 quality %
Chloride ion: 1ppm
Surface area after the mensuration etching in the vertical 5 μ m of copper foil surface * horizontal 5 μ m zones.Consequently the surface area of Copper Foil is 38[μ m
2].
Surface roughness (the Rzjis: 10 height of nao-and micro relief) of the Copper Foil after the mensuration etching.Consequently the surface roughness of Copper Foil is 0.25[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 5.60.Calculating formula is as described below.
E={38/(5×5)}/0.25=6.08
Calculate the etch quantity of copper foil surface based on above-mentioned general formula (2).Consequently the etch quantity of copper foil surface is 0.3 μ m.
The peel strength of Copper Foil is 0.9kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 4.5 μ m on a small quantity.
embodiment 4
In embodiment 4, the etching condition of the etch processes of the glassy surface of electrolytic copper foil is changed as described below, in addition, carry out the test identical with embodiment 3.
Etching condition
The temperature of fluid composition for etching: 35 ℃
Expulsion pressure: 0.2MPa
Injecting time: 1 minute
Surface area after the mensuration etching in the vertical 5 μ m of copper foil surface * horizontal 5 μ m zones.Consequently the surface area of Copper Foil is 45[μ m
2].
Surface roughness (the Rzjis: 10 height of nao-and micro relief) of the Copper Foil after the mensuration etching.Consequently the surface roughness of Copper Foil is 0.45[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 3.70.Calculating formula is as described below.
E={45/(5×5)}/0.45=4.0
Calculate the etch quantity of copper foil surface based on above-mentioned general formula (2).Consequently the etch quantity of copper foil surface is 0.65 μ m.
The peel strength of Copper Foil is 0.95kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 5.0 μ m on a small quantity.
comparative example 1
In comparative example 1, the following electrolytic copper foil that uses a surface to be roughened in advance, in addition, carry out the test identical with embodiment 1.
Electrolytic copper foil
Thickness: 12 μ m
Trade name: MITSUI MINING& SMELTING CO., LTD. manufactures, 3EC-VLP
Utilize scanning tunnel microscope to observe the surface of above-mentioned electrolytic copper foil with the multiplying power of 30000 times.Fig. 2 is the 3-D view of the copper foil surface that now observes.
Measure the surface area in 5 μ m * horizontal 5 μ m zones of indulging of copper foil surface.Consequently the surface area of Copper Foil is 36.2[μ m
2].
Measure the surface roughness (Rzjis: 10 height of nao-and micro relief) of Copper Foil.Consequently the surface roughness of Copper Foil is 3.65[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 0.40.Calculating formula is as described below.
E={36.2/(5×5)}/3.65=0.40
The peel strength of Copper Foil is 0.90kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 9.8 μ m on a small quantity.Fig. 4 is based on the cross-section photograph of the wiring of electron microscope.
comparative example 2
In comparative example 2, the following electrolytic copper foil that uses a surface to be roughened in advance, in addition, carry out the test identical with embodiment 1.
Electrolytic copper foil
Thickness: 12 μ m
Trade name: FURUKAWA ELECTRIC CO., LTD. manufactures, FV-WS
Measure the surface area in 5 μ m * horizontal 5 μ m zones of indulging of copper foil surface.Consequently the surface area of Copper Foil is 33.8[μ m
2].
Measure the surface roughness (Rzjis: 10 height of nao-and micro relief) of Copper Foil.Consequently the surface roughness of Copper Foil is 2.20[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 0.61.Calculating formula is as described below.
E={33.8/(5×5)}/2.20=0.61
The peel strength of Copper Foil is 0.85kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 9.5 μ m on a small quantity.
comparative example 3
In comparative example 3, the following electrolytic copper foil that uses a surface to be roughened in advance, in addition, carry out the test identical with embodiment 1.
Electrolytic copper foil
Thickness: 12 μ m
Trade name: JX Nippon Mining& Metals Corporation manufactures, HLPLC
Measure the surface area in 5 μ m * horizontal 5 μ m zones of indulging of copper foil surface.Consequently the surface area of Copper Foil is 32.2[μ m
2].
Measure the surface roughness (Rzjis: 10 height of nao-and micro relief) of Copper Foil.Consequently the surface roughness of Copper Foil is 2.05[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 0.63.Calculating formula is as described below.
E={32.2/(5×5)}/2.05=0.63
The peel strength of Copper Foil is 0.85kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 9.3 μ m on a small quantity.
comparative example 4
In comparative example 4, the following electrolytic copper foil that uses a surface to be roughened in advance, in addition, carry out the test identical with embodiment 1.
Electrolytic copper foil
Thickness: 12 μ m
Trade name: FUKUDA METAL FOIL& POWDER Co., LTD. manufactures, SV
Measure the surface area in 5 μ m * horizontal 5 μ m zones of indulging of copper foil surface.Consequently the surface area of Copper Foil is 31.3[μ m
2].
Measure the surface roughness (Rzjis: 10 height of nao-and micro relief) of Copper Foil.Consequently the surface roughness of Copper Foil is 1.85[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 0.68.Calculating formula is as described below.
E={31.3/(5×5)}/1.85=0.68
The peel strength of Copper Foil is 0.70kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 9.0 μ m on a small quantity.
comparative example 5
In comparative example 5, fluid composition used in the etch processes of the glassy surface of electrolytic copper foil is changed as described below, in addition, carry out the test identical with embodiment 1.
The composition of fluid composition for etching
Hydrogen peroxide: 1.3 quality %
Sulfuric acid: 5 quality %
5-Aminotetrazole: 0.35 quality %
Trade name: Mitsubishi Gas Chemical Company, Inc. manufactures, CPE-900
Surface area in the vertical 5 μ m of the copper foil surface after the mensuration etching * horizontal 5 μ m zones.Consequently the surface area of Copper Foil is 36[μ m
2].
Surface roughness (the Rzjis: 10 height of nao-and micro relief) of the Copper Foil after the mensuration etching.Consequently the surface roughness of Copper Foil is 0.75[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 5.60.Calculating formula is as described below.
E={36/(5×5)}/0.75=1.92
Calculate the etch quantity of copper foil surface based on above-mentioned general formula (2).Consequently the etch quantity of copper foil surface is 1.5 μ m.
The peel strength of Copper Foil is 0.50kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 6.5 μ m on a small quantity.
comparative example 6
In comparative example 6, except the glassy surface of not etching electrolytic copper foil, carry out the test identical with embodiment 1.
Surface area in the vertical 5 μ m of copper foil surface (untreated) * horizontal 5 μ m zones is 25[μ m
2].
Measure the surface roughness (Rzjis: 10 height of nao-and micro relief) of Copper Foil (untreated).Consequently the surface roughness of Copper Foil is 0.1[μ m].
Calculate closely sealed enhancing coefficient E based on above-mentioned general formula (1).Consequently closely sealed enhancing coefficient E is 5.60.Calculating formula is as described below.
E={25/(5×5)}/0.1=10
The peel strength of Copper Foil is 0.20kgf/cm.
The Xian Kuan Minus of the wiring pattern after the removal crystal seed layer is 4.5 μ m on a small quantity.
Embodiment 1～4 and comparative example 1～6 be the results are shown in to following table 1.
[table 1]
Embodiment 1～4 compares closely sealed enhancing coefficient E with comparative example 1～5 large.
Embodiment 1,2 compares Copper Foil with comparative example 1～6 peel strength with 4 is large.
Embodiment 3 equates with the peel strength of comparative example 1, and the peel strength of comparing Copper Foil with comparative example 2～6 is large.
Embodiment 1～4 compares wiring pattern Xian Kuan Minus with comparative example 1～5 is on a small quantity little.
It is few that embodiment 1～4 and comparative example 5 are compared etch quantity.
Adaptation between Copper Foil of the present invention and insulating substrate is good.
The Xian Kuan Minus of the wiring pattern of Copper Foil of the present invention is on a small quantity little, therefore can form trickle wiring pattern.
Copper Foil of the present invention can be well is the printed circuit board (PCB) below 20 μ m for the live width of wiring pattern.
Claims (13)
1. a copper foil for printed circuit board, wherein, the value of the closely sealed enhancing coefficient E shown in the following general formula (1) at least one surface is 2.5～8,
10 height of the nao-and micro relief of the surface area/copper foil surface of E=Copper Foil ... (1)
Wherein, the average surface area of the unit area of the surface area of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope to observe described Copper Foil surperficial.
2. copper foil for printed circuit board according to claim 1, wherein, the etched processing in the surface of described Copper Foil.
3. copper foil for printed circuit board according to claim 2, wherein, the etch quantity of the described copper foil surface shown in following general formula (2) is below 1 μ m,
Etch quantity [μ m]=(quality of Copper Foil after the quality-etching of the front Copper Foil of etching)/(density of etching area * copper) ... (2)
In formula, the density of copper is 8.96g/cm
3.
4. according to the described copper foil for printed circuit board of claim 2 or 3, wherein, described etch processes fluid composition used comprise in the group of selecting free hydrogen peroxide, sulfuric acid, halide ion and tetrazolium class to form more than a kind.
5. according to the described copper foil for printed circuit board of any one in claim 1～3, wherein, the surface of described Copper Foil is not processed with metal, silane coupler or bonding agent beyond copper.
6. a copper-clad laminated board, it possess insulating substrate and
Be laminated in the described copper foil for printed circuit board of any one described insulating substrate surface, in claim 1～3.
7. a printed circuit board (PCB), it possesses copper-clad laminated board claimed in claim 6.
8. printed circuit board (PCB) according to claim 7, it utilizes semi-additive process to be formed with wiring pattern.
9. printed circuit board (PCB) according to claim 7, it utilizes subtractive process to be formed with wiring pattern.
10. printed circuit board (PCB) according to claim 8 or claim 9, wherein, the live width of described wiring pattern is below 20 μ m.
11. the manufacture method of a copper foil for printed circuit board, wherein, carry out etch processes at least one surface of Copper Foil, makes the value of the closely sealed enhancing coefficient E shown in following general formula (1) reach 2.5～8,
10 height of the nao-and micro relief of the surface area/copper foil surface of E=Copper Foil ... (1)
Wherein, the average surface area of the unit area of the surface area of Copper Foil is Copper Foil vertical 1 μ m * horizontal 1 μ m, the surface area of Copper Foil is the value obtained while utilizing scanning tunnel microscope to observe described Copper Foil surperficial.
12. the manufacture method of copper foil for printed circuit board according to claim 11, wherein, described etch processes fluid composition used comprise in the group of selecting free hydrogen peroxide, sulfuric acid, halide ion and tetrazolium class to form more than a kind.
13. the manufacture method of copper foil for printed circuit board according to claim 12, wherein, described etching comprises with fluid composition
0.2 the hydrogen peroxide of～1.5 quality %,
0.5 the sulfuric acid of～3.0 quality %,
0.3 the halide ion of～3ppm and
0.01 the tetrazolium class of～0.3 quality %.
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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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382745A (en) * | 2017-05-19 | 2019-10-25 | 三井金属矿业株式会社 | Roughening treatment copper foil, band carrier copper foil, copper-clad laminated board and printed circuit board |
| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1520469A (en) * | 2001-06-25 | 2004-08-11 | ������ѧ��ʽ���� | Surface treatment agent for copper and copper alloy |
| WO2005095951A1 (en) * | 2004-04-02 | 2005-10-13 | Mitsui Mining & Smelting Co., Ltd. | Method for evaluating bonding strength of roughened surface of copper foil |
| CN1938456A (en) * | 2004-04-02 | 2007-03-28 | 三井金属矿业株式会社 | Copper foil and its manufacturing method |
| JP2009105286A (en) * | 2007-10-24 | 2009-05-14 | Mitsui Mining & Smelting Co Ltd | Surface-processed copper foil |
| CN101932439A (en) * | 2007-10-24 | 2010-12-29 | 宇部兴产株式会社 | Metal foil laminated polyimide resin substrate |
| TW201139752A (en) * | 2010-01-22 | 2011-11-16 | Furukawa Electric Co Ltd | Surface-treated copper foil, method for producing same, and copper clad laminated board |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
-
2013
- 2013-06-05 KR KR1020130064989A patent/KR102128954B1/en active IP Right Grant
- 2013-06-06 CN CN201310223952.5A patent/CN103476198B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1520469A (en) * | 2001-06-25 | 2004-08-11 | ������ѧ��ʽ���� | Surface treatment agent for copper and copper alloy |
| WO2005095951A1 (en) * | 2004-04-02 | 2005-10-13 | Mitsui Mining & Smelting Co., Ltd. | Method for evaluating bonding strength of roughened surface of copper foil |
| CN1938456A (en) * | 2004-04-02 | 2007-03-28 | 三井金属矿业株式会社 | Copper foil and its manufacturing method |
| JP2009105286A (en) * | 2007-10-24 | 2009-05-14 | Mitsui Mining & Smelting Co Ltd | Surface-processed copper foil |
| CN101932439A (en) * | 2007-10-24 | 2010-12-29 | 宇部兴产株式会社 | Metal foil laminated polyimide resin substrate |
| TW201139752A (en) * | 2010-01-22 | 2011-11-16 | Furukawa Electric Co Ltd | Surface-treated copper foil, method for producing same, and copper clad laminated board |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382745A (en) * | 2017-05-19 | 2019-10-25 | 三井金属矿业株式会社 | Roughening treatment copper foil, band carrier copper foil, copper-clad laminated board and printed circuit board |
| CN110382745B (en) * | 2017-05-19 | 2021-06-25 | 三井金属矿业株式会社 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
| 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 |
Also Published As
| Publication number | Publication date |
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| CN103476198B (en) | 2018-03-06 |
| KR102128954B1 (en) | 2020-07-01 |
| KR20130137104A (en) | 2013-12-16 |
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