WO2010147013A1 - 銅箔及びその製造方法 - Google Patents
銅箔及びその製造方法 Download PDFInfo
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- WO2010147013A1 WO2010147013A1 PCT/JP2010/059602 JP2010059602W WO2010147013A1 WO 2010147013 A1 WO2010147013 A1 WO 2010147013A1 JP 2010059602 W JP2010059602 W JP 2010059602W WO 2010147013 A1 WO2010147013 A1 WO 2010147013A1
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- WIPO (PCT)
- Prior art keywords
- zinc
- copper foil
- nickel
- layer
- peel strength
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12847—Cr-base component
- Y10T428/12854—Next to Co-, Fe-, or Ni-base component
Definitions
- the present invention relates to a copper foil for a flexible printed circuit board on which a polyimide resin layer is formed on a copper foil, and in particular, has excellent adhesion (normal peel strength, heat-resistant peel strength) between the copper foil and the polyimide resin layer, and is tin-resistant plated.
- the present invention relates to a copper foil that is suitable for a flexible printed circuit board that has liquid properties and that can be finely patterned.
- the property required for the fine patterning of copper foil is not only a problem of adhesion to such a resin.
- it is required to have excellent acid resistance and tin plating solution resistance.
- Patent Documents 3, 4, and 5 there are many patent documents (see Patent Documents 3, 4, and 5).
- JP 2002-217507 A JP-A-56-155592 JP 2005-344174 A JP 2007-165694 A JP 2007-7937 A
- the present invention has been made in view of the above-mentioned problems, and the object thereof is excellent in adhesiveness (normal peel strength, heat-resistant peel strength) between the copper foil and the polyimide resin layer, and tin-resistant.
- An object of the present invention is to provide a copper foil suitable for a flexible printed circuit board having plating solution properties and capable of forming a fine pattern of wiring.
- a copper foil comprising a plated layer containing nickel and zinc on a copper foil made of electrolytic copper foil or rolled copper foil, and a chromium plated layer on the plated layer containing nickel and zinc.
- Zinc in the plating layer to be contained is composed of a zero-valent metal state and a divalent oxidation state, and the ratio of metal zinc in the total zinc is 50% or less.
- the copper foil as described in 1 above, wherein the plating layer containing nickel and zinc is 50 to 1500 ⁇ g / dm 2 in total of nickel and zinc.
- the copper foil according to 1 above, wherein the plating layer containing nickel and zinc is 100 to 1000 ⁇ g / dm 2 in total of nickel and zinc. 4.
- the copper foil according to any one of the above 1 to 4 further comprising a mixed silane coupling agent layer of amino alkoxysilane and tetraalkoxysilane on the outermost layer having a chromium plating layer.
- the amount of zinc on the outermost layer measured by XPS is below the detection limit or 2 at% or less, and the amount of chromium on the outermost layer is 5 to 30 at%.
- the amount of zinc on the outermost layer measured by XPS is below the detection limit or 1 at% or less, and the amount of chromium on the outermost layer is 8 to 30 at%. Of copper foil.
- the present invention provides a copper foil that is excellent in adhesion (normal peel strength, heat-resistant peel strength) between a copper foil and a polyimide resin layer, has a tin plating solution resistance, and can be used for fine patterning of wiring. It has an excellent effect of being able to.
- the electrolytic copper foil uses a rotating metal cathode drum and an insoluble metal anode (anode) surrounding the cathode drum, which is disposed at a position approximately half the lower side of the cathode drum.
- a copper electrolyte is allowed to flow between the electrodes, and an electric potential is applied between them to electrodeposit copper on the cathode drum.
- the electrodeposited copper is peeled off from the cathode drum and the copper is continuously removed.
- a foil is being manufactured.
- the rolled copper foil is produced by repeatedly melting and casting an ingot by repeating many times of rolling and annealing.
- the present invention provides a plating layer containing nickel and zinc (hereinafter referred to as “nickel-zinc plating layer”) on a copper foil made of electrolytic copper foil or rolled copper foil, and chromium on the nickel-zinc plating layer. It is copper foil provided with the plating layer. As described above, the copper foil provided with these coating layers is already known. However, the problem is that, when tin plating is performed on the known copper foil in this way, the tin plating solution penetrates between the polyimide resin layer and the copper foil and reduces the peel strength of the copper foil. . Due to the high erodibility of the tin plating solution, if the surface treatment is partially eroded, it may lead to circuit peeling, which is a very big problem.
- a nickel-zinc plating layer is formed on a copper foil made of an electrolytic copper foil or a rolled copper foil. It was found that there was a cause in the nickel-zinc plating layer coated on. This nickel-zinc plating layer is not a simple alloy plating layer. Examination of the chemical state of zinc in the nickel-zinc plating layer revealed that the nickel-zinc plating layer was composed of zinc oxide and / or zinc hydroxide and metallic zinc.
- This ratio of zinc oxide and / or zinc hydroxide to metallic zinc can be achieved by changing the nickel-zinc plating conditions.
- the conditions for nickel-zinc plating are shown below, but can be implemented by those skilled in the art within the range shown.
- it goes without saying that it cannot be achieved on a regular basis without the intention of adjusting the ratio of zinc oxide and / or zinc hydroxide to metallic zinc. That is, it is found that the ratio of zero-valent metal zinc in the total zinc composed of the zero-valent metal state and the divalent oxidized state is a direct cause of the infiltration of the tin plating solution.
- the present inventor has found that the infiltration of the tin plating solution can be suppressed by setting the chemical state of zinc in the nickel-zinc plating layer, that is, the ratio of metallic zinc in the total zinc to 50% or less.
- the chemical state of zinc in the nickel-zinc plating layer that is, the ratio of metallic zinc in the total zinc to 50% or less.
- the metal zinc ratio in the plating layer can be lowered.
- the ratio of metallic zinc is 50% or less.
- the presence of zinc oxide in the nickel-zinc plating layer means that it is preferable to prevent the penetration of the tin plating solution.
- it is difficult to change the chemical state of all zinc in the nickel-zinc plating to zinc oxide it is possible to reduce metallic zinc as much as possible to about 10% or even about 5%.
- the condition of nickel-zinc plating is adjusted to a condition in which the ratio of zinc oxide and / or zinc hydroxide to metal zinc in metal zinc is 50% or less within a range of steady conditions.
- the chemical state of the zinc of the present invention can be achieved.
- the nickel-zinc plating layer further has a total of nickel and zinc of 50 to 1500 ⁇ g / dm 2. Further, the nickel-zinc plating layer has a total of nickel and zinc of 100 to 1000 ⁇ g / dm 2. It is desirable that In the present invention, the presence of a nickel-zinc plating layer is an essential requirement.
- the nickel-zinc plating layer may be a normal amount, but if the amount of this plating layer is less than 50 ⁇ g / dm 2 , the plating effect as a whole is lost, and the nickel-zinc plating layer is inevitably formed. This is because the normal peel strength, heat peel strength, chemical resistance, and tin plating resistance are poor. Moreover, it does not need to exist excessively. Even if it exists in excess, the effect is saturated and only the cost is increased. In this sense, it can be said that the upper limit is preferably 1500 ⁇ g / dm 2 .
- the nickel ratio in the nickel-zinc plating layer is 40 to 80 wt%.
- the nickel ratio is less than 40 wt%, the chemical resistance and heat resistance are lowered, and when the nickel ratio is more than 80 wt%, the etching property (fine etching property) deteriorates when a circuit is formed. % Can be said to be desirable.
- nickel ratio exceeds 90 wt%, heat resistance will also fall. This is considered to be because when the nickel ratio is increased, the amount of zinc is relatively decreased, and the heat resistance of zinc is lowered. Therefore, it is desirable to determine the nickel ratio in consideration of these points.
- the present invention further includes a plating layer containing nickel and zinc on a copper foil made of electrolytic copper foil or rolled copper foil, and a chromium plating layer on the plating layer containing nickel and zinc.
- a copper foil in which a mixed silane coupling agent layer of amino-based alkoxysilane and tetraalkoxysilane is further formed on the outermost layer having a plating layer. Adhesiveness to various polyimide resins can be obtained by the mixed silane coupling agent layer of amino alkoxysilane and tetraalkoxysilane.
- the amount of metallic zinc in the outermost layer measured by XPS is 2 at% or less
- the amount of chromium in the outermost layer is 5 to 30 at%
- the amount of metallic zinc in the outermost layer measured by XPS. Is 1 at% or less, and provides the copper foil in which the outermost layer has a chromium content of 8 to 30 at%. If the amount of zinc exceeds 2 at%, the normal peel strength decreases, so it is desirable that the above numerical value be the upper limit.
- the amount of metallic zinc in the outermost layer be as small as possible. If possible, 0% is good, but there is actually a slight presence of about 0.01 at%.
- the amount of zinc metal in the outermost layer is effective for the resistance to tin plating solution.
- the outermost layer on which the chromium plating layer is formed naturally has a lot of chromium, but oxygen, carbon, nitrogen, nickel, copper, and zinc are also present in addition to this.
- Appropriate amounts of chromium and zinc are effective in improving the normal peel strength.
- the above range shows the amount.
- the amount of chromium is effective in improving the normal peel strength, and there is no particular upper limit, but the upper limit is 40% in production.
- the chromium content is 5 to 30 at%.
- the presence of chromium is not as effective as the nickel-zinc plating layer, but is also effective for the resistance to tin plating solution.
- the outermost layer on which the chromium plating layer is formed depends on the degree of the chromium plating layer, the depth measured by XPS is about several nm (2 to 3 nm). Since the film thickness is very thin as described above, it is very difficult to measure the film thickness. However, this film is not necessarily a uniform film, and it is assumed that there are many minute holes. Therefore, it is considered that the outermost layer does not necessarily contain only chromium, but the component of the nickel-zinc plating layer serving as the underlying layer is exposed through the holes. Therefore, it is expected that the outermost layer is a state in which chromium, zinc, nickel, copper, and oxides thereof exist.
- an electrolytic copper foil having a surface roughness 10-point average roughness (Rz) of 2.5 ⁇ m or less, but it is not particularly limited to this condition.
- Rz 10-point average roughness
- a rough surface (matt surface) or a glossy surface with minute irregularities can be applied to the copper foil of the present invention.
- rolled copper foil has the surface excellent in smoothness from the characteristic of a manufacturing process, it can apply similarly to this invention.
- high etching accuracy can be obtained by setting the surface roughness of the copper foil to 1.5 ⁇ m or less, and further to 1.0 ⁇ m or less. That is, in order to increase the etching accuracy, it can be said that it is preferable to make the surface roughness of the raw copper foil smaller. Usually, no roughening treatment is required.
- the glossy surface of rolled copper foil or electrolytic copper foil is suitable.
- the rough surface of the electrolytic copper foil can be set to the above condition, that is, the surface roughness can be 1.5 ⁇ m or less. Therefore, the rough surface can be used.
- the electrolytic copper foil and the rolled copper foil are continuously manufactured and wound around a coil, but the copper foil obtained as described above is further subjected to surface treatment or coating treatment of the present invention such as electrochemical or chemical or resin. (Coating) can be applied and used for printed wiring boards and the like.
- the thickness of the copper foil is required to be 18 ⁇ m or less, more preferably 3 to 12 ⁇ m in order to be used as a high-density wiring, but the copper foil treatment of the present invention is not limited to such thickness. It can also be applied to ultra thin foils or thick copper foils.
- nickel-zinc plating is used as a heat-resistant layer.
- cobalt, molybdenum, phosphorus, boron, tungsten or the like to the film in which the chemical state of zinc is controlled, the ratio of these can be controlled. It is expected that the same effect as the present invention can be obtained.
- These are suitably selected according to the use of the copper foil of a printed wiring board, and this invention includes all these.
- the means for forming the polyimide resin layer is not particularly limited.
- polyamic acid varnish (polyamic acid obtained by addition polymerization of aromatic diamines and aromatic dianhydrides in a solution state as a raw material) Can be used.
- This polyamic acid varnish is applied onto the electrolytic copper foil or rolled copper foil of the present invention, and further dried to form a polyamic acid layer as a polyimide precursor layer.
- the obtained polyamic acid layer is imidized by heating to 300 ° C. to 400 ° C. in an inert atmosphere such as nitrogen to form a polyimide resin layer.
- the thickness of the polyimide resin layer is not particularly limited, but is usually 10 to 50 ⁇ m.
- the electrolytic copper foil and the rolled copper foil are used, and the nickel-zinc plated layer and the chromium plated layer of the present invention are formed on the electrolytic copper foil or the rolled copper foil.
- An example of the electrochemical treatment liquid is as follows. (Nickel-zinc plating solution composition and plating conditions 1) Ni: 10-40g / L Zn: 0.5-7 g / L H 2 SO 4 : 2 to 20 g / L Bath temperature: normal temperature to 65 ° C Current density Dk: 10 to 50 A / dm 2 Plating time: 1 to 4 seconds (Nickel-zinc plating solution composition and plating conditions 2) Ni: 10-40g / L Zn: 0.5 to 20 g / L pH: 3.0-4.0 Bath temperature: normal temperature to 65 ° C Current density Dk: 1 to 15 A / dm 2 Plating time: 1 to 4 seconds (cobalt-molybdenum plating solution composition and plating conditions) Co: 10-40 g / L Mo: 10-40
- Amino silane coupling agent 0.2-1.2 vol%
- Amino silane coupling agent 0.2-1.2 vol%
- ⁇ -aminopropyltriethoxysilane N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, and the like.
- Tetraalkoxysilane 0.2-0.6 vol%
- TEOS tetraethoxysilane
- Example 1 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni content 65 ⁇ g / dm 2
- Zn content 60 ⁇ g / dm 2
- ratio of metallic zinc in total zinc in nickel-zinc plating layer 45%
- Ni ratio in nickel-zinc plating layer 52 wt%
- XPS The zinc content of the outermost layer measured by 1 was 1 at%
- the chromium content of the outermost layer was 8 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions. The results are shown in Table 1.
- the normal peel strength was 0.9 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 2 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni amount 80 [mu] g / dm 2
- Zn amount 65 [mu] g / dm 2
- Ni - ratio of zinc metal in the total zinc in the zinc plating layer 40%
- nickel - Ni ratio in the galvanized layer 55 wt% XPS
- the amount of zinc on the outermost layer measured by 1 was 1.2 at%, and the amount of chromium on the outermost layer was 9 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 0.9 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 3 As the copper foil, an 18 ⁇ m electrolytic copper foil having a surface roughness Rz 0.7 ⁇ m was used. This electrolytic copper foil was degreased and washed with water, followed by pickling and washing, and then plated under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the Ni content 55 ⁇ g / dm 2
- the Zn content 80 ⁇ g / dm 2
- the ratio of metal zinc in the total zinc in the nickel-zinc plating layer 35%
- the Ni ratio in the nickel-zinc plating layer 41 wt%
- XPS XPS
- the amount of zinc in the outermost layer measured by 1 was 1.2 at%
- the amount of chromium in the outermost layer was 8 at%.
- a chromium plating layer was formed on the nickel-zinc plated copper foil under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 0.8 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer (normal peel strength, heat-resistant peel strength) and tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 4 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the amount of zinc on the outermost layer measured by 1.9 was 1.9 at%, and the amount of chromium on the outermost layer was 8 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 0.7 kN / m
- the peel strength retention after aging was> 80%
- the permeation amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 5 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was performed under the above-described Ni—Zn plating conditions, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni amount 300 ⁇ g / dm 2
- Zn amount 80 ⁇ g / dm 2
- ratio of metallic zinc in total zinc in nickel-zinc plating layer 45%
- Ni ratio in nickel-zinc plating layer 79 wt%
- XPS The amount of zinc on the outermost layer measured by 1 was 0.8 at%
- the amount of chromium on the outermost layer was 10 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 0.9 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 6 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni content 110 ⁇ g / dm 2
- Zn content 110 ⁇ g / dm 2
- ratio of metallic zinc in total zinc in nickel-zinc plating layer 40%
- Ni ratio in nickel-zinc plating layer 50 wt%
- XPS X-ray photoelectron spectroscopy
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 1.3 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 7 As the copper foil, a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used. The rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the Ni amount 700 ⁇ g / dm 2
- the Zn amount 300 ⁇ g / dm 2
- the ratio of metallic zinc in the total zinc in the nickel-zinc plating layer 30%
- the Ni ratio in the nickel-zinc plating layer 70 wt%
- XPS The amount of zinc on the outermost layer measured by 2 was 0.2 at%
- the amount of chromium on the outermost layer was 20 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 1.2 kN / m
- the peel strength retention after aging was> 80%
- the permeation amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- Example 8 As the copper foil, an 18 ⁇ m electrolytic copper foil having a surface roughness Rz 0.7 ⁇ m was used. This electrolytic copper foil was degreased and washed with water, followed by pickling and washing, and then plated under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was carried out under the conditions of Ni—Zn plating 1 shown above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni amount 650 ⁇ g / dm 2
- Zn amount 350 ⁇ g / dm 2
- ratio of metallic zinc in total zinc in nickel-zinc plating layer 20%
- Ni ratio in nickel-zinc plating layer 65 wt%
- XPS The zinc content of the outermost layer measured by 1 was 1 at%
- the chromium content of the outermost layer was 20 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 1.
- the normal peel strength was 1.2 kN / m
- the peel strength retention after aging was> 80%
- the permeation amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesion to the polyimide resin layer normal peel strength, heat-resistant peel strength
- tin plating solution resistance were all excellent.
- the etching property was also excellent.
- a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used as the copper foil.
- the rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions.
- Nickel-zinc plating was performed under the Ni—Zn plating 2 conditions described above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the Ni content 200 ⁇ g / dm 2
- the Zn content 200 ⁇ g / dm 2
- the ratio of metallic zinc in the total zinc in the nickel-zinc plating layer 80%
- the Ni ratio in the nickel-zinc plating layer 50 wt%
- XPS XPS
- the amount of zinc in the outermost layer measured in step 6 was 6 at%
- the amount of chromium in the outermost layer was 2 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 2.
- the normal peel strength was 0.2 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was> 2 ⁇ m.
- the adhesion to the polyimide resin layer was poor
- the tin plating solution resistance was poor.
- a rolled copper foil of 18 ⁇ m having a surface roughness Rz of 0.7 ⁇ m was used as the copper foil.
- the rolled copper foil was degreased and washed with water, followed by pickling and washing, followed by plating under the above-mentioned nickel-zinc plating conditions.
- Nickel-zinc plating was performed under the Ni—Zn plating 2 conditions described above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- Ni amount 200 [mu] g / dm 2
- Zn amount 0 Pg / dm 2
- Ni - ratio of zinc metal in the total zinc in the galvanized layer -%
- nickel - Ni ratio in the galvanized layer 100 wt%
- XPS The amount of zinc on the outermost layer measured by 1 was 0 at%
- the amount of chromium on the outermost layer was 3 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 2.
- the normal peel strength was 0.7 kN / m
- the peel strength retention after aging was 40%
- the permeation amount of the tin plating solution was ⁇ 1 ⁇ m.
- the adhesiveness (heat resistant peel strength) with the polyimide resin layer was poor.
- Example 3 As the copper foil, an 18 ⁇ m electrolytic copper foil having a surface roughness Rz 0.7 ⁇ m was used. This electrolytic copper foil was degreased and washed with water, followed by pickling and washing, and then plated under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was performed under the Ni—Zn plating 2 conditions described above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the Ni content 370 ⁇ g / dm 2
- the Zn content 80 ⁇ g / dm 2
- the ratio of metallic zinc in the total zinc in the nickel-zinc plating layer 90%
- the Ni ratio in the nickel-zinc plating layer 82 wt%
- XPS XPS
- the zinc content of the outermost layer measured by the above was 0.6 at%
- the chromium content of the outermost layer was 4 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 2.
- the normal peel strength was 0.5 kN / m
- the peel strength retention after aging was> 80%
- the permeation amount of the tin plating solution was> 2 ⁇ m.
- the adhesion to the polyimide resin layer was poor, and the tin plating solution resistance was poor.
- Example 4 As the copper foil, an 18 ⁇ m electrolytic copper foil having a surface roughness Rz 0.7 ⁇ m was used. This electrolytic copper foil was degreased and washed with water, followed by pickling and washing, and then plated under the above-mentioned nickel-zinc plating conditions. Nickel-zinc plating was performed under the Ni—Zn plating 2 conditions described above, a chromium plating layer was formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed.
- the Ni content 200 ⁇ g / dm 2
- the Zn content 20 ⁇ g / dm 2
- the ratio of metallic zinc in the total zinc in the nickel-zinc plating layer 70%
- the Ni ratio in the nickel-zinc plating layer 91 wt%
- XPS XPS
- the amount of zinc on the outermost layer measured by 1 was 0.3 at%
- the amount of chromium on the outermost layer was 3 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 2.
- the normal peel strength was 0.3 kN / m
- the peel strength retention after aging was> 80%
- the permeation amount of the tin plating solution was> 2 ⁇ m.
- the adhesion to the polyimide resin layer was poor, and the tin plating solution resistance was poor.
- Example 5 As the copper foil, an 18 ⁇ m electrolytic copper foil having a surface roughness Rz 0.7 ⁇ m was used. The electrolytic copper foil was degreased and washed with water, followed by pickling and washing, followed by cobalt-molybdenum alloy plating. Cobalt-molybdenum alloy plating was performed under the above-described Co—Mo plating conditions, a chromium plating layer was further formed under the above conditions, and a mixed silane coupling agent layer of amino and TEOS was further formed. As a result, the Co content: 440 ⁇ g / dm 2 , the Mo content: 290 ⁇ g / dm 2 , and the chromium content of the outermost layer measured by XPS were 1 at%.
- the copper foil thus produced was measured for the normal peel strength, the peel strength retention after aging, and the penetration amount of the tin plating solution under the above conditions.
- the results are shown in Table 2.
- the normal peel strength was 0.4 kN / m
- the peel strength retention after aging was> 80%
- the penetration amount of the tin plating solution was> 2 ⁇ m.
- the adhesion to the polyimide resin layer was poor, and the tin plating solution resistance was poor.
- the present invention provides a copper foil that is excellent in adhesion (normal peel strength, heat-resistant peel strength) between a copper foil and a polyimide resin layer, has a tin plating solution resistance, and can be used for fine patterning of wiring. It is useful as a copper foil for a flexible printed circuit board that forms a polyimide resin layer.
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Abstract
Description
従来、粗化処理し樹脂との接着性を向上させた電解銅箔が使用されていたが、この粗化処理のために銅箔のエッチング性が著しく損なわれ、高アスペクト比でのエッチングが困難となり、十分なファインパターン化ができないという問題が生じた。
しかしながら、電解銅箔のロープロファイル化は電解銅箔と絶縁性のポリイミド層との間の密着強度を低下させるという問題がある。このため、ハイレベルなファインパターン化の要求はあるが、一方では所期の接着強度を維持することができず、配線がポリイミド層から加工段階で剥離してしまうなどの問題が発生した。
最近の傾向として、ポリイミド系樹脂層との密着性に大きな関心が寄せられており、その特許文献も、多数ある(特許文献3、4、5参照)。
このように、銅箔上にポリイミド系樹脂層を形成するフレキシブルプリント基板用銅箔に対して、上記の錫めっき液の染み込みの問題を含め、総合的に問題を解決しない限り、良好な特性を持つ銅箔を得ているとは言えない。
1.電解銅箔又は圧延銅箔からなる銅箔上に、ニッケルと亜鉛を含有するめっき層及び当該ニッケルと亜鉛を含有するめっき層上にクロムめっき層を備えた銅箔であって、ニッケルと亜鉛を含有するめっき層における亜鉛は0価の金属状態と2価の酸化状態からなり、総亜鉛中の金属亜鉛の比率が50%以下であることを特徴とする銅箔
2.ニッケルと亜鉛を含有するめっき層が、ニッケル及び亜鉛の合計で50~1500μg/dm2であることを特徴とする上記1記載の銅箔
3.ニッケルと亜鉛を含有するめっき層が、ニッケル及び亜鉛の合計で100~1000μg/dm2であることを特徴とする上記1記載の銅箔
4.ニッケルと亜鉛を含有するめっき層中のニッケル比{ニッケル量/(ニッケル量+亜鉛量)}が、40~80wt%であることを特徴とする上記1~3のいずれか一項に記載の銅箔
5.クロムめっき層を有する最表層上にさらに、アミノ系アルコキシシラン及びテトラアルコキシシランの混合系シランカップリング剤層を備える上記1~4のいずれか一項に記載の銅箔
6.XPSで測定した最表層の亜鉛量が検出限界以下、もしくは2at%以下であり、同最表層のクロム量が5~30at%であることを特徴とする上記1~5のいずれか一項に記載の銅箔
7.XPSで測定した最表層の亜鉛量が検出限界以下、もしくは1at%以下であり、同最表層のクロム量が8~30at%であることを特徴とする上記1~5のいずれか一項に記載の銅箔、を提供する。
また、圧延銅箔は、溶解鋳造したインゴットを、多数回の圧延と焼鈍を繰返して製造するものである。これらの電解銅箔又は圧延銅箔は、フレキシブルプリント基板用銅箔として既に知られた材料であり、本願発明はこれらに全て適用できる。
錫めっき液の持つ高い侵食性よって、表面処理が部分的にでも侵食を受けると、回路剥離につながる可能性があり、非常に大きな問題である。
このニッケル-亜鉛めっき層は、単純な合金めっき層ではない。ニッケル-亜鉛めっき層における亜鉛の化学状態を調べると、ニッケル-亜鉛めっき層は、亜鉛酸化物及び/または亜鉛水酸化物と金属亜鉛から構成されることが分かった。
下記の実施例において、具体的に説明するが、金属亜鉛の比率が50%を超えると、錫めっき液の染み込み発生を抑制することが難しくなる。したがって、金属亜鉛の比率を50%以下とするものである。
しかし、下記の実施例に示すように、金属亜鉛を極力低減させることによって錫めっき液の染み込み発生を抑制するという効果は、極限まで低減させる必要はないことを知るべきである。したがって、ニッケル-亜鉛めっきの条件は、定常の条件の範囲で、亜鉛酸化物及び/または亜鉛水酸化物と、金属亜鉛中の金属亜鉛の比率を50%以下とする条件に調節することにより、本願発明の亜鉛の化学状態を達成できる。
ニッケル-亜鉛めっき層は、通常の量で良いのであるが、このめっき層の量が50μg/dm2未満であると全体量としての、めっきの効果が無くなり、必然的にニッケル-亜鉛めっき層が持つ、常態ピール強度、耐熱ピール強度、耐薬品性、さらに耐錫めっき性が劣る結果となるからである。
また、過剰に存在する必要もない。過剰に存在しても効果が飽和し、コスト高になるだけである。この意味から、1500μg/dm2を上限とすることが望ましいと言える。
なお、ニッケル比が90wt%を超えるようになると、耐熱性も低下する。これは、ニッケル比が増加すると、相対的に亜鉛量が減少し、亜鉛が持つ耐熱性を低下させるということが起因すると考えられる。したがって、これらの点を勘案して、ニッケル比率を決定するのが望ましい。
このアミノ系アルコキシシラン及びテトラアルコキシシランの混合系シランカップリング剤層によって様々なポリイミド系樹脂への密着性を得ることが可能となる。
また、耐錫めっき液性のためには、最表層の金属亜鉛量はできるだけ少ない方が望ましい。可能であれば0%であることが良いのであるが、実際上0.01at%程度のわずかな存在がある。最表層の金属亜鉛量であれば、耐錫めっき液性に有効である。
上記の通り、クロム量は、常態ピール強度の向上に効果があり、特に上限はないのであるが、製作上40%が限度である。通常クロム量を5~30at%とするのが、望ましいと言える。また、クロムの存在は、ニッケル-亜鉛めっき層ほどの効果を有するものではないが、耐錫めっき液性にも有効である。
したがって、最表層は、必ずしもクロムだけが存在するだけではなく、その下地となるニッケル-亜鉛めっき層の成分が、孔を通して露出している状態と考えられる。したがって、最表層は、クロム、亜鉛、ニッケル、銅、これらの酸化物が存在する状態であると予想される。
一般に、銅箔の表面粗さを1.5μm以下に、さらには1.0μm以下とすることにより、高いエッチング精度を得ることができる。すなわちエッチング精度を上げるためには、原銅箔の表面粗さをより小さくすることが好ましいと言える。通常、粗化処理は不要である。
電解銅箔及び圧延銅箔は連続的に製造されコイルに巻かれるが、上記のようにして得た銅箔は、その後さらに本発明の電気化学的若しくは化学的又は樹脂等の表面処理又は被覆処理(コーティング)を施してプリント配線板等に使用することができる。
また、本発明ではニッケル-亜鉛めっきを耐熱層としたが、亜鉛の化学状態が制御された皮膜中にコバルトやモリブデン、リン、ホウ素、タングステン等を添加してこれらの比率を制御することによっても本発明と同様の効果が得られると期待される。これらは、プリント配線基板の銅箔の用途に応じて適宜選択されるものであり、本発明はこれらを全て包含する。
このポリアミック酸ワニスを、本発明の電解銅箔又は圧延銅箔上に塗布し、さらに乾燥してポリイミド前駆体層としてのポリアミック酸層を形成する。得られたポリアミック酸層を、窒素等の不活性雰囲気下で300°C~400°Cに加熱してイミド化し、ポリイミド系樹脂層を形成する。
ポリイミド系樹脂層の厚みは特に限定されないが、通常10~50μmとする。また、ポリアミック酸ワニスには、必要に応じて従来公知の添加剤を配合してもよい。このようにして得られるフレキシブルプリント基板においては、本発明の電解銅箔又は圧延銅箔とポリイミド系樹脂層との接着強度が良好なものとなる。
(ニッケル-亜鉛めっき液組成とめっき条件1)
Ni:10~40g/L
Zn:0.5~7g/L
H2SO4:2~20g/L
浴温度:常温~65°C
電流密度Dk:10~50A/dm2
めっき時間:1~4秒
(ニッケル-亜鉛めっき液組成とめっき条件2)
Ni:10~40g/L
Zn:0.5~20g/L
pH:3.0~4.0
浴温度:常温~65°C
電流密度Dk:1~15A/dm2
めっき時間:1~4秒
(コバルト-モリブデンめっき液組成とめっき条件)
Co:10~40g/L
Mo:10~40g/L
pH:4.0~5.0
浴温度:常温~40°C
電流密度Dk:1~15A/dm2
めっき時間:1~10秒
CrO3:200~250g/L(実施例・比較例では、250g/L)
H2SO4:2~3g/L(実施例・比較例では、2.5g/L)
浴温度:50~60℃(実施例・比較例では、55℃)
めっき液には必要に応じ、従来公知の添加剤重クロム酸ナトリウムや重クロム酸カリウム、三価のクロム塩、珪フッ化ナトリウム等を配合しても良い。
(カップリング剤組成)
アミノ系シランカップリング剤:0.2~1.2vol%
例えば、γ-アミノプロピルトリエトキシシランやN-β(アミノエチル)γ-アミノプロピルトリメトキシシラン等。
テトラアルコキシシラン:0.2~0.6vol%
例えば、TEOS(テトラエトキシシラン)等。
(樹脂組成)
ポリイミド:宇部興産製(UワニスA、樹脂厚み:30μm)
(ピール強度試験)
常態ピール強度:幅3mm、膜厚9μm銅箔の180°引き剥がし試験
エージング後のピール強度:150°C、7日間のエージング後、ピール強度測定
(錫めっき液染み込み性試験)
錫めっき液:ロームアンドハース製LT-34
70°C、5分浸漬後、侵食量を測定
(XPS解析)
Kratos製AXIS-HSにより測定した。材料をスパッタリングして掘り進めながらXPS測定したが、本発明ではスパッタリングする前の最表面の測定値に注目した。
なお、本発明との対比のために、比較例を掲載した。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:65μg/dm2、Zn量:60μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:45%、ニッケル-亜鉛めっき層におけるNi比:52wt%、XPSで測定した最表層の亜鉛量:1at%、同最表層のクロム量:8at%となった。
この結果を表1に示す。
本実施例1における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:80μg/dm2、Zn量:65μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:40%、ニッケル-亜鉛めっき層におけるNi比:55wt%、XPSで測定した最表層の亜鉛量:1.2at%、同最表層のクロム量:9at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は0.9kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例2における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの電解銅箔を使用した。この電解銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:55μg/dm2、Zn量:80μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:35%、ニッケル-亜鉛めっき層におけるNi比:41wt%、XPSで測定した最表層の亜鉛量:1.2at%、同最表層のクロム量:8at%となった。
このようにして製造した銅箔を、上記の条件で、常態ピール強度の測定、エージング後のピール強度保持率、及び錫めっき液の染み込み量を測定した。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は0.8kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例3における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:220μg/dm2、Zn量:300μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:12%、ニッケル-亜鉛めっき層におけるNi比:42wt%、XPSで測定した最表層の亜鉛量:1.9at%、同最表層のクロム量:8at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は0.7kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例4における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:300μg/dm2、Zn量:80μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:45%、ニッケル-亜鉛めっき層におけるNi比:79wt%、XPSで測定した最表層の亜鉛量:0.8at%、同最表層のクロム量:10at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は0.9kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例5における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:110μg/dm2、Zn量:110μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:40%、ニッケル-亜鉛めっき層におけるNi比:50wt%、XPSで測定した最表層の亜鉛量:0.1at%、同最表層のクロム量:23at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は1.3kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例6における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:700μg/dm2、Zn量:300μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:30%、ニッケル-亜鉛めっき層におけるNi比:70wt%、XPSで測定した最表層の亜鉛量:0.2at%、同最表層のクロム量:20at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は1.2kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例7における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの電解銅箔を使用した。この電解銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき1の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:650μg/dm2、Zn量:350μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:20%、ニッケル-亜鉛めっき層におけるNi比:65wt%、XPSで測定した最表層の亜鉛量:1at%、同最表層のクロム量:20at%となった。
この結果を表1に示す。
上記表1に示すように、常態ピール強度は1.2kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は<1μmであった。
本実施例8における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)、耐錫めっき液性が、いずれも優れていた。また、表には示さないが、エッチング性にも優れていた。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき2の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:200μg/dm2、Zn量:200μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:80%、ニッケル-亜鉛めっき層におけるNi比:50wt%、XPSで測定した最表層の亜鉛量:6at%、同最表層のクロム量:2at%となった。
この結果を表2に示す。
上記表2に示すように、常態ピール強度は0.2kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は>2μmであった。
比較例1における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)が悪く、耐錫めっき液性がいずれも悪かった。
銅箔として表面粗さRz0.7μmである18μmの圧延銅箔を使用した。この圧延銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき2の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:200μg/dm2、Zn量:0μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:-%、ニッケル-亜鉛めっき層におけるNi比:100wt%、XPSで測定した最表層の亜鉛量:0at%、同最表層のクロム量:3at%となった。
この結果を表2に示す。
上記表2に示すように、常態ピール強度は0.7kN/m、エージング後のピール強度保持率は40%、錫めっき液の染み込み量は<1μmであった。
比較例2における上記の試験結果では、ポリイミド系樹脂層との接着性(耐熱ピール強度)が悪かった。
銅箔として表面粗さRz0.7μmである18μmの電解銅箔を使用した。この電解銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき2の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:370μg/dm2、Zn量:80μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:90%、ニッケル-亜鉛めっき層におけるNi比:82wt%、XPSで測定した最表層の亜鉛量:0.6at%、同最表層のクロム量:4at%となった。
この結果を表2に示す。
上記表2に示すように、常態ピール強度は0.5kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は>2μmであった。
比較例3における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)が悪く、耐錫めっき液性がいずれも悪かった。
銅箔として表面粗さRz0.7μmである18μmの電解銅箔を使用した。この電解銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、上記ニッケル-亜鉛めっきの条件でめっきを行った。上記に示したNi-Znめっき2の条件で、ニッケル-亜鉛めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Ni量:200μg/dm2、Zn量:20μg/dm2、ニッケル-亜鉛めっき層における総亜鉛中の金属亜鉛の比率:70%、ニッケル-亜鉛めっき層におけるNi比:91wt%、XPSで測定した最表層の亜鉛量:0.3at%、同最表層のクロム量:3at%となった。
この結果を表2に示す。
上記表2に示すように、常態ピール強度は0.3kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は>2μmであった。
比較例4における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)が悪く、耐錫めっき液性がいずれも悪かった。
銅箔として表面粗さRz0.7μmである18μmの電解銅箔を使用した。この電解銅箔を、脱脂及び水洗処理、続いて酸洗・水洗処理した後、コバルト-モリブデン合金めっきを行った。上記に示したCo-Moめっきの条件で、コバルト-モリブデン合金めっきを実施し、さらに上記の条件でクロムめっき層を形成し、さらにアミノ系及びTEOSの混合系シランカップリング剤層を形成した。その結果、Co量:440μg/dm2、Mo量:290μg/dm2、XPSで測定した最表層のクロム量:1at%となった。
この結果を表2に示す。
上記表2に示すように、常態ピール強度は0.4kN/m、エージング後のピール強度保持率は>80%、錫めっき液の染み込み量は>2μmであった。
比較例5における上記の試験結果では、ポリイミド系樹脂層との接着性(常態ピール強度、耐熱ピール強度)が悪く、耐錫めっき液性がいずれも悪かった。
Claims (7)
- 電解銅箔又は圧延銅箔からなる銅箔上に、ニッケルと亜鉛を含有するめっき層及び当該ニッケルと亜鉛を含有するめっき層上にクロムめっき層を備えた銅箔であって、ニッケルと亜鉛を含有するめっき層における亜鉛は、0価の金属状態と2価の酸化状態からなり、総亜鉛中の0価の金属状態の亜鉛の比率が50%以下であることを特徴とする銅箔。
- ニッケルと亜鉛を含有するめっき層が、ニッケル及び亜鉛の合計で50~1500μg/dm2であることを特徴とする請求項1記載の銅箔。
- ニッケルと亜鉛を含有するめっき層が、ニッケル及び亜鉛の合計で100~1000μg/dm2であることを特徴とする請求項1記載の銅箔。
- ニッケルと亜鉛を含有するめっき層中のニッケル比{ニッケル量/(ニッケル量+亜鉛量)}が、40~80wt%であることを特徴とする請求項1~3のいずれか一項に記載の銅箔。
- クロムめっき層を有する最表層上にさらに、アミノ系アルコキシシラン及びテトラアルコキシシランの混合系シランカップリング剤層を備える請求項1~4のいずれか一項に記載の銅箔。
- XPSで測定した最表層の亜鉛量が検出限界以下、もしくは2at%以下であり、同最表層のクロム量が5~30at%であることを特徴とする請求項1~5のいずれか一項に記載の銅箔。
- XPSで測定した最表層の亜鉛量が検出限界以下、もしくは1at%以下であり、同最表層のクロム量が8~30at%であることを特徴とする請求項1~5のいずれか一項に記載の銅箔。
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JP4955105B2 (ja) | 2008-12-26 | 2012-06-20 | Jx日鉱日石金属株式会社 | 電子回路用の圧延銅箔又は電解銅箔及びこれらを用いた電子回路の形成方法 |
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JP7033905B2 (ja) * | 2017-02-07 | 2022-03-11 | Jx金属株式会社 | 表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法 |
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JP5470487B1 (ja) * | 2013-05-29 | 2014-04-16 | Jx日鉱日石金属株式会社 | 銅箔、それを用いた半導体パッケージ用銅張積層体、プリント配線板、プリント回路板、樹脂基材、回路の形成方法、セミアディティブ工法、半導体パッケージ用回路形成基板及び半導体パッケージ |
WO2014192895A1 (ja) * | 2013-05-29 | 2014-12-04 | Jx日鉱日石金属株式会社 | 銅箔、キャリア付銅箔、銅張積層体、プリント配線板、半導体パッケージ用回路形成基板、半導体パッケージ、電子機器、樹脂基材、回路の形成方法、セミアディティブ工法、プリント配線板の製造方法 |
KR101822251B1 (ko) | 2013-05-29 | 2018-01-25 | 제이엑스금속주식회사 | 구리박, 캐리어 부착 구리박, 구리 피복 적층체, 프린트 배선판, 반도체 패키지용 회로 형성 기판, 반도체 패키지, 전자 기기, 수지 기재, 회로의 형성 방법, 세미 애디티브 공법, 프린트 배선판의 제조 방법 |
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US11337315B2 (en) | 2018-04-27 | 2022-05-17 | Jx Nippon Mining & Metals Corporation | Surface treated copper foil, copper clad laminate, and printed circuit board |
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Also Published As
Publication number | Publication date |
---|---|
MY159142A (en) | 2016-12-15 |
JPWO2010147013A1 (ja) | 2012-12-06 |
EP2444530A1 (en) | 2012-04-25 |
KR101343667B1 (ko) | 2013-12-20 |
TWI484072B (zh) | 2015-05-11 |
US20120135266A1 (en) | 2012-05-31 |
EP2444530A4 (en) | 2013-01-02 |
KR20120023744A (ko) | 2012-03-13 |
JP5399489B2 (ja) | 2014-01-29 |
CN102803575B (zh) | 2016-02-03 |
TW201105826A (en) | 2011-02-16 |
CN102803575A (zh) | 2012-11-28 |
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