CN110475909B - Surface-treated copper foil and copper-clad laminate using same - Google Patents
Surface-treated copper foil and copper-clad laminate using same Download PDFInfo
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- CN110475909B CN110475909B CN201880020021.6A CN201880020021A CN110475909B CN 110475909 B CN110475909 B CN 110475909B CN 201880020021 A CN201880020021 A CN 201880020021A CN 110475909 B CN110475909 B CN 110475909B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
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- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- 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
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Abstract
The present invention provides a surface-treated copper foil which is excellent in line-to-line and line-width miniaturization, etching property, laser processing property and thin foil handling property, has few pinholes, and has high tensile strength. The surface-treated copper foil of the present invention has a tensile strength of 400 to 700MPa, a tensile strength of 300MPa or more after heating at 220 ℃ for 2 hours, a foil thickness of 7 μm or less, an open area ratio (Sdr) of 25 to 120% on one side, and the number of pinholes having a diameter of 30 μm or more being 20 pinholes/m2The following.
Description
Technical Field
The present invention relates to a surface-treated copper foil which is suitable for a printed wiring board having a high-density wiring circuit (fine pattern) and is excellent in laser processability, and a copper-clad laminate using the same.
Background
A printed wiring board is a copper-clad laminate produced by placing a thin copper foil for forming a surface circuit on the surface of an electrically insulating substrate made of glass epoxy resin, polyimide resin, or the like, and then heating and pressing the copper foil. Then, via-hole drilling and via-hole plating are sequentially performed on the copper-clad laminate, and then the copper foil of the copper-clad laminate is etched to form a wiring pattern having a desired line width and a desired line pitch. Finally, a solder resist coating, exposure, through hole plating, or other finishing treatment is performed to remove uncured solder resist with caustic soda or the like in order to expose plating of the connection portion of the electronic component.
In general, an electrolytic copper foil obtained by depositing a copper foil 101 on a roll 102 using an electrolytic deposition apparatus shown in fig. 1 and peeling the copper foil 101 is used as the copper foil used in this case. The initial surface of electrolytic deposition (smooth surface, hereinafter, referred to as "S surface") obtained by peeling from the roller 102 is relatively smooth, and the final surface of electrolytic deposition (rough surface, hereinafter, referred to as "M surface") which is the opposite surface generally has irregularities. Generally, the M-plane is roughened to improve adhesion to the substrate resin.
Recently, a printed wiring board, particularly a build-up (build-up) wiring board, has been manufactured by bonding an adhesive resin such as an epoxy resin to a roughened surface of a copper foil in advance, forming the adhesive resin into an insulating resin layer in a semi-cured state (B stage) to form a resin-coated copper foil, using the resin-coated copper foil as a copper foil for forming a surface circuit, and thermally pressing one side of the insulating resin layer of the copper foil to a substrate (insulating substrate). In this build-up wiring substrate, it is desired to highly integrate various electronic components, and in response to this, a wiring pattern is also required to have a high density, and thus a wiring pattern requiring a fine line width and a fine line pitch, a so-called fine pattern, has been gradually developed. For example, a printed wiring board having high-density ultrafine wiring with a line width and a line pitch of about 15 μm is required as a multilayer board used for a server, a router, a communication base station, a vehicle-mounted board, and the like, or a multilayer board for a smartphone.
With the increase in density and miniaturization of such wiring substrates, it has become increasingly difficult to form fine circuits by a subtractive process, and instead, a semi-additive process (MSAP) has been used. In the MSAP method, an extra thin copper foil is formed as a power supply layer on a resin layer, and then pattern copper plating is performed on the extra thin copper foil. Next, the extra thin copper foil is removed by rapid etching, thereby forming a desired wiring.
In the MSAP method, a thin copper foil with a carrier is generally used. The thin copper foil with carrier was used in the following manner: a release layer and a thin copper foil are formed in this order on one surface of a copper foil (carrier copper foil) as a carrier, and the surface of the thin copper foil becomes a roughened surface. Then, the roughened surface is superposed on a resin substrate, the whole is thermocompression bonded, and then the carrier copper foil is peeled off and removed to expose the bonding side of the thin copper foil to the carrier copper foil, and a predetermined wiring pattern is formed on the bonding side.
In order to make interlayer connection in the build-up wiring board, a hole called a through hole is opened, and the opening is often performed by irradiation with laser light. In the MSAP method, a method called direct laser processing is used as follows: the copper foil and the resin are instantaneously perforated by directly irradiating the copper foil with laser light.
The surface of the copper foil with a carrier used in the MSAP method to be bonded to a resin substrate is generally an M-surface, and the laser-processed surface (S-surface) is smooth and insufficient in laser absorption, and therefore brown oxidation treatment (etching roughening treatment) is required as a pretreatment for laser processing. In view of this, patent document 1 proposes a copper foil having a laser-light absorbing layer made of chromium, cobalt, nickel, iron, or the like on the laser-processed surface in order to improve the laser processability of the S-surface, thereby improving the laser processability. However, the thin copper foil of the copper foil with a carrier is produced by using a general copper sulfate bath plating bath, and has a problem of a large number of pinholes.
Patent document 2 proposes a copper foil in which pinholes are suppressed by uniformly forming a nickel layer, a zinc layer, and a chromate layer as intermediate layers. However, since the intermediate layer (release layer) is formed on the glossy surface of the carrier foil, the intermediate layer irradiated with the laser after the carrier foil is peeled is smooth and does not easily absorb the light of the laser, and the laser processability is poor. Further, since the copper foil with a carrier is used, there is a problem that it takes time and labor to peel the copper foil with a carrier, and the workability is poor.
Patent document 3 proposes a copper foil with a carrier, in which variation in roughness on the intermediate layer side of the thin copper foil is suppressed, thereby improving laser processability and etching properties. However, the thin copper foil of the copper foil with a carrier is produced by using a general copper sulfate bath plating bath, and has a problem of a large number of pinholes.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-75443
Patent document 2: international publication No. 2015/030256
Patent document 3: japanese laid-open patent publication No. 2014-208480
Disclosure of Invention
Problems to be solved by the invention
In the MSAP method, a copper foil with a carrier is used, but the copper foil with a carrier has the following problems.
The number of pinholes is large, and the manufacturing yield is low.
The intermediate layer irradiated with the laser beam after peeling the carrier foil is smooth and hardly absorbs the laser beam, and thus the laser processability is poor. Therefore, brown oxidation treatment (etching roughening treatment) is required as pretreatment for laser processing.
The peeling step of the carrier foil takes time and labor, which increases the manufacturing cost.
Because of such problems, new materials are desired to replace the copper foil with a carrier. In view of these problems, an object of the present invention is to provide a surface-treated copper foil which has high tensile strength in a normal state and after heating, does not cause wrinkles even in a carrier foil-free thin foil, is applicable to an MSAP method, is excellent in laser processability (direct laser processing), etching properties and thin foil handling properties, has few pinholes, and is suitable for a high-density wiring circuit.
Means for solving the problems
The present inventors have made extensive studies, and in the course of this, have found that a roughened surface having "25% to 120% Sdr" is suitable for direct laser processing. Further, it was found that the surface-treated copper foil of the present invention has a tensile strength of 400MPa to 700MPa in the normal state and a tensile strength measured at ordinary temperature after heating at 220 ℃ for 2 hoursA surface-treated copper foil having a foil thickness of 7 μm or less and a degree of 300MPa or more, wherein the ratio of developed area (Sdr) of at least one surface is 25 to 120%, and the number of pinholes having a diameter of 30 μm or more is 20 pinholes/m2The present invention has been completed based on the following findings that the film has excellent etching properties, laser processability (direct laser processing), and workability of a thin foil, has few pinholes, and is suitable for a high-density wiring circuit.
In the present invention, the normal state means a state in which the surface-treated copper foil is left at room temperature (about 25 ℃) without heat history such as heat treatment. Normal tensile strength can be determined at room temperature by IPC-TM-650. The tensile strength after heating can be measured at room temperature in the same manner as the tensile strength in the normal state after heating the surface-treated copper foil to 220 ℃ and holding it for 2 hours, and then naturally cooling it to room temperature.
When the normal tensile strength is 400MPa to 700MPa, the workability and etching properties are good. If the normal tensile strength is less than 400MPa, wrinkles are generated when the foil product is conveyed, and therefore, the handling property is poor, and if the tensile strength is more than 700MPa, foil breakage is likely to occur during production by deposition from a roll, and the production is not suitable. When the tensile strength measured at room temperature after heating is 300MPa or more, crystal grains are fine and etching properties are good after heating in the step of laminating the substrates. When the tensile strength after the same heating is 300MPa or less, crystal grains become large and are not easily dissolved by etching, and thus the etching property is deteriorated.
The foil thickness of the surface-treated copper foil may be 7 μm or less, or 6 μm or less. When the foil thickness of the surface-treated copper foil exceeds 7 μm, the degree of opening by a low-energy laser tends to be deteriorated. When the foil thickness of the surface-treated copper foil is 7 μm or less, particularly 6 μm or less, the laser processability, particularly the processability in laser irradiation of low energy of about 8W tends to be high.
In the present invention, the foil thickness refers to a film thickness of a copper foil produced by electrolytic deposition at a stage before laser processing after surface treatment such as formation of a laser light absorption layer, formation of a roughened layer, formation of a nickel layer, formation of a zinc layer, chromate treatment, and formation of a silane coupling layer, which will be described later, is performed as necessary. The foil thickness can be determined as mass thickness by means of an electronic balance.
In the present invention, by setting the ratio of the developed area (Sdr) of at least one surface to 25% to 120%, the direct laser processability can be improved when the surface is set as the laser-irradiated surface.
The spread area ratio (Sdr) is defined by the following equation, which is a ratio of the surface area increased by the surface properties based on an ideal plane having the size of the measurement region.
[ numerical formula 1]
Here, x and y in the formula are plane coordinates, and z is a coordinate in the height direction. z (x, y) represents the coordinate of a certain point, and the slope at the coordinate point is obtained by differentiating the coordinate. Further, a is a plane area of the measurement region.
The spread area ratio (Sdr) can be obtained by measuring and evaluating the difference in roughness of the surface of the copper foil by a three-dimensional white interference microscope, a Scanning Electron Microscope (SEM), an electron beam three-dimensional roughness analyzer, or the like. Generally, Sdr tends to increase as the spatial complexity of the surface properties increases, regardless of the change in the surface roughness Sa.
Here, the principle of the direct laser processing will be explained. The following equation holds when the reflectance on the surface of the copper foil is represented by r, the absorptance is represented by μ, and the transmittance is represented by τ.
r+μ+τ＝1
In the direct laser processing, a laser beam, usually CO, is selected so that τ is 0 for the copper foil2A gas laser, and the like, wherein r + μ is 1. When the laser beam is absorbed in a uniform intensity distribution, the temperature distribution on the beam center axis (Z axis) is expressed by the following equation, where the beam radius is a.
[ numerical formula 2]
Here, x and y in the formula are plane coordinates, and z is a coordinate in the height direction. In addition, P is the absorbed laser power [ J/s ]]And x is K/rho.C [ cm ] thermal diffusivity2/S]K is the thermal conductivity [ J/cm · s · K]Rho is the density [ g/cm ]3]C is specific heat [ J/g.K ]]And t is the laser irradiation time [ s ]]And a is the beam radius [ cm ]]。
The temperature rises with time, but saturates for a certain time, and the temperature at this time is represented by the following equation.
[ numerical formula 3]
As can be seen from the above formula, the temperature increases as the energy of the laser beam absorbed by the surface of the copper foil increases. This is because the absorbed energy of the laser beam amplifies the atomic vibration and converts it into heat. In the direct laser processing, the copper foil at the laser irradiation portion is melted by the thermal energy to perform the hole forming processing. In order to improve the accuracy and efficiency of direct laser processing, it is necessary to reduce the reflectance on the surface of the copper foil or to improve the absorption as seen from the above formula.
In the conventional MSAP method, the absorption rate of the surface of copper after carrier foil peeling is low, and therefore direct laser processing is dealt with by increasing the absorption rate by roughening the surface by brown oxidation treatment, but the brown oxidation treatment step takes labor and time, and therefore, there is a problem in view of the production cost. As a result of extensive studies, it has been found that the direct laser processability can be improved when the surface is a laser-irradiated surface by setting the ratio of the developed area (Sdr) of at least one surface of the copper foil to 25% to 120%. When the surface has an Sdr of 25% to 120%, a highly complex irregular shape of 1 μm or less is formed. When a copper foil having such a shape is irradiated with laser light, diffuse reflection increases, and the absorption rate of the laser light increases. Further, it is considered that the reflectance is decreased by forming an oxide film by activating the outermost layer of the copper foil by the complicated surface roughness shape, the thermoelectric conductivity is decreased by increasing the surface area of the oxide film layer, and the direct laser processability is improved by increasing the temperature of the laser irradiated portion as compared with the conventional one. If the Sdr of the laser-processed surface is less than 25%, the reflectivity is high and the laser absorption is poor, so that the laser absorption tends to be poor. If the Sdr is more than 120%, the defect that the hole is filled again with molten copper tends to occur, and the laser processability is deteriorated.
Further, it is known that when a copper foil is made thin, the performance of a circuit board is deteriorated if pinholes are generated, but in the present invention, 20 pinholes having a diameter of 30 μm or more are obtained2The following copper foil can suppress the performance degradation of the circuit board.
The number of pinholes is determined by cutting the copper foil into suitable sizes, for example, 200mm × 200mm, marking the pinholes by, for example, a light transmission method, confirming the diameter with an optical microscope, and counting the number of the holes having a diameter of 30 μm or more. Based on the obtained number of pinholes, the area per unit (m) can be calculated2) Number of pinholes (number/m)2)。
Effects of the invention
According to the present invention, a copper foil excellent in etching properties, laser processability, thin foil handling properties, and pinhole resistance can be provided. Further, a surface-treated copper foil can be provided which is applicable to the MSAP method even for an unsupported copper foil because of its high tensile strength in the normal state and after heating.
Drawings
FIG. 1 is a view showing a conventional electrolytic copper foil deposition apparatus.
FIG. 2 is a view showing an apparatus for depositing an electrolytic copper foil having a cathodic reduction step.
FIG. 3 is a graph showing the relationship between the numerical aperture of the laser beam and the number of pinholes in examples and comparative examples.
Fig. 4 is a graph showing the relationship between the normal tensile strength and the number of defective wrinkles in examples and comparative examples.
Detailed Description
The surface-treated copper foil of the present invention has a spreading area ratio (Sdr) of 25 to 120%, but if the spreading area ratio (Sdr) is 30 to 80%, stress is presentThe photoprocessability tends to be further improved. In addition, when the foil thickness of the surface-treated copper foil is 7 μm or less, particularly 6 μm or less, the spread area ratio (Sdr) is preferably 30% to 80%, and the number of pinholes having a diameter of 30 μm or more is preferably 10/m2The following. If the number of pinholes with a diameter of more than 30 μm exceeds 10/m2The performance tends to be lowered when the resin composition is applied to a circuit board.
The surface-treated copper foil of the present invention is preferably such that Y becomes 25.0% to 65.5%, x becomes 0.30% to 0.48%, and Y becomes 0.28% to 0.41% in a Yxy color system of the laser-processed surface. The laser processed surface of the surface-treated copper foil satisfies the above-mentioned spread area ratio (Sdr), and further when the processed surface is in the range of 25.0% to 65.5% in Y, 0.30% to 0.48% in x, and 0.28% to 0.41% in Y in the Yxy color system, the laser absorption property becomes better, and the laser processability is very good.
The Yxy color system can be measured by a device such as a colorimeter (colorimeter) according to JISZ8722, for example.
As described above, since the surface of the copper foil used in the MSAP method to be bonded to the resin substrate is an M-surface and the laser-processed surface is smooth and insufficient in laser absorption, brown oxidation treatment (etching roughening treatment) is performed as pretreatment for laser processing. In the present invention, laser processability can be improved without performing brown oxidation treatment.
The conditions and method for producing the surface-treated copper foil of the present invention will be described below.
(1) Production of electrolytic copper foil
The copper foil of the present invention is produced, for example, by using an aqueous sulfuric acid-copper sulfate solution as an electrolytic solution, supplying the electrolytic solution between an insoluble anode made of titanium covered with a platinum group element or an oxide element thereof and a titanium cathode roll disposed opposite to the anode, and passing a direct current between the anode and the cathode roll while rotating the cathode roll at a fixed speed, thereby depositing copper on the surface of the cathode roll, and continuously winding the deposited copper by peeling it off from the surface of the cathode roll.
In the present invention, it is preferable to produce the electrolytic copper foil so that the deposition potential of copper in the surface of the cathode roll is uniform without variation. For this purpose, for example, a method of forming a foil in a state where no oxide film is present on the surface of a titanium roll is mentioned. As an example, a cathodic reduction step may also be employed. As shown in fig. 1, in a conventional apparatus for manufacturing an electrolytic copper foil, an electrolytic roll 102 serving as a cathode is polished by a polishing wheel 103, thereby removing an oxide film formed on the surface of the roll. On the other hand, the cathodic reduction step is a step of removing an oxide film by an electrolytic solution (dilute sulfuric acid) 106 of a cathodic reduction apparatus 105 as shown in the apparatus for depositing an electrolytic copper foil of fig. 2, for example, instead of the polishing wheel 103 of the apparatus for depositing an electrolytic copper foil of fig. 1. By removing the oxide film by the roll 102 and the cathode reduction apparatus 105, it is expected that initial deposition of copper occurs uniformly on the surface of the titanium roll and pinholes are reduced. In the production of a copper foil using a conventional titanium roll shown in fig. 1, since the titanium oxide film on the surface of the titanium roll has a non-uniform thickness, the deposition potential of copper varies within the roll surface, and pinholes tend to occur when the copper foil is made thin. By adopting the cathode reduction step, the cathode reduction current density is increased, and pinholes can be reduced. This is because the reduction of titanium oxide is further advanced by increasing the cathodic reduction current density, and the distribution of the deposition potential of copper in the titanium roll surface is not uneven, and pinholes are likely to be suppressed.
In the production of an electrolytic copper foil, ethylene thiourea, polyethylene glycol, tetramethyl thiourea, polyacrylamide, etc. may be added as an additive to be added to the electrolyte solution. By increasing the addition amount of ethylene thiourea and tetramethyl thiourea, the normal tensile strength and the tensile strength after heating can be increased. When the normal tensile strength is 400MPa to 700MPa, the workability and etching properties are good. If the normal tensile strength is less than 400MPa, the workability is poor, and if it exceeds 700MPa, the foil tends to break, and the production is not suitable. When the tensile strength measured at room temperature after heating at 220 ℃ for 2 hours is 300MPa or more, crystal grains are fine and etching properties are good even after heating in the lamination of the substrates. When the tensile strength after heating measured in the same manner is 300MPa or less, crystal grains become large and are not easily dissolved by etching, and thus the etching property is deteriorated.
(2) Surface treatment of copper foil
< laser absorbing layer formation treatment >
Next, the copper foil obtained above was subjected to surface treatment for forming a laser light absorbing layer. In the present invention, a plating layer having a concavo-convex shape is formed on one surface of a copper foil by a pulse current. This surface is a laser-processed surface when a circuit is produced by the MSAP method using a copper foil. The surface on which the laser light absorbing layer is formed may be a deposition start surface (S-surface) or a deposition end surface (M-surface) in the electrolytic copper foil production step. In general, the surface to be bonded to the resin substrate (roughened surface) is an M-surface and the laser-processed surface is an S-surface in many cases, but in the present invention, the surface to be bonded to the resin substrate may be an S-surface roughened surface and the laser-processed surface may be an M-surface. That is, the roughened layer may be formed on the initial surface (S-surface) of electrolytic deposition in the production process of the electrolytic copper foil.
In the present invention, it was found that direct laser processing can be achieved without performing brown oxidation treatment by having an appropriate surface area so that the ratio Sdr of the developed area of the M-plane or the S-plane to be a laser processing surface is 25% to 120%. Further, the etching factor can be improved by forming the roughened layer on the initial surface of electrolytic deposition in the production process of the electrolytic copper foil.
Copper sulfate pentahydrate, sulfuric acid, hydroxyethyl cellulose (HEC), polyethylene glycol (PEG), thiourea, and the like may be added as a plating bath composition for forming a laser light absorbing layer. By applying positive pulse currents having different current values in two stages, the additive to be applied changes according to the deposition potentials of the corresponding two stages, and a complicated uneven shape can be formed. This makes it possible to obtain a precipitation surface having excellent laser absorption. Specifically, in the stepped pulse current having a current value in 1 stage (Ion1) >2 stage (Ion2), the Sdr of the M-plane tends to increase when the current value in 1 stage (Ion1) or the time in 1 stage (ton1) is increased. By applying such two-stage pulse currents at fixed time intervals (toff), a surface shape having an Sdr value which is excellent in laser processability can be obtained.
Sdr in the range of 25% to 120%The laser processability is improved. Such a foil has a fine uneven shape of about 2 μm or less on the surface of the surface-treated copper foil, and the laser absorptivity increases. If the Sdr is less than 25%, the laser absorption is poor and the laser processability is poor. If Sdr is greater than 120%, CO2The absorption rate of light of the laser wavelength decreases, and laser processability decreases. In addition, when the time interval (toff) of the pulse current is increased, Y is decreased in the Yxy color system. If Sdr is in the range of 25% to 120%, and Y is in the range of 15.0% to 85.0% in the Yxy color system, laser processability is good. If Y is less than 15% or more than 85%, laser processability tends to be lowered. When Sdr increases, the laser numerical aperture tends to increase, and when the Y value decreases, the laser numerical aperture tends to increase. The laser processability is particularly good if the Sdr of the laser irradiation face is in the range of 25% to 120%, and Y is 25.0% to 65.5%, x is 0.30% to 0.48%, and Y is 0.28% to 0.41% in the Yxy color system.
< formation of roughened surface >
A roughened layer having a fine uneven surface is formed on the surface of the copper foil opposite to the laser-processed surface by electrodeposition of fine copper particles. The roughened layer is formed by electroplating, and it is preferable to add a chelating agent to the plating bath, the concentration of the chelating agent being preferably 0.1g/L to 5 g/L. Examples of the chelating agent include: chelating agents such as DL-malic acid, EDTA (ethylenediaminetetraacetic acid) sodium solution, sodium gluconate, and diethylenetriaminepentaacetic acid pentasodium (DTPA).
Copper sulfate, sulfuric acid and molybdenum may also be added to the electrolytic bath. By adding molybdenum, etching properties can be improved. Usually, the copper concentration is 13g/L to 72g/L, the sulfuric acid concentration is 26g/L to 133g/L, the liquid temperature is 18 ℃ to 67 ℃, and the current density is 3A/dm2To 67A/dm2And the treatment time is 1 second to 1 minute 55 seconds.
< formation of Nickel layer, Zinc layer, chromate treatment layer >
In the present invention, it is preferable that a nickel layer and a zinc layer are further formed in this order on the roughened surface. The zinc layer serves to prevent deterioration of the substrate resin due to a reaction between the thin copper foil and the substrate resin and oxidation of the surface of the thin copper foil when the thin copper foil is thermocompression bonded to the resin substrate, thereby improving the bonding strength with the substrate. The nickel layer also functions as a base layer of the zinc layer to prevent the zinc of the zinc layer from thermally diffusing to the copper foil (electrolytic copper plating layer) side when thermocompression bonding the resin substrate, thereby effectively exhibiting the above-described function of the zinc layer.
The nickel layer and the zinc layer can be formed by applying a known electrolytic plating method or electroless plating method. In addition, the nickel layer can be formed by pure nickel or phosphorus-containing nickel alloy.
Further, it is preferable to further chromate the surface of the zinc layer because an antioxidation layer is formed on the surface. As the chromate treatment to be applied, there may be mentioned any known method, for example, the method disclosed in Japanese patent laid-open No. 60-86894. By making the amount of chromium 0.01mg/dm as converted2To 0.3mg/dm2The chromium oxide and the hydrate thereof adhere to the copper foil, and thereby the copper foil can be provided with excellent rust preventive ability.
< silane treatment >
Further, when the surface treated with the chromate treatment is further subjected to a surface treatment using a silane coupling agent, a functional group having a strong affinity with an adhesive is given to the surface of the copper foil (the surface on the side to be bonded to the substrate), and therefore, the bonding strength between the copper foil and the substrate is further improved, and the rust prevention property and moisture absorption heat resistance of the copper foil are further improved, which is preferable.
Examples of the silane coupling agent include vinyl silane, epoxy silane, styrene silane, methacryloxy silane, acryloxy silane, amino silane, ureide silane, chloropropyl silane, mercapto silane, sulfide silane, and isocyanate silane. These silane coupling agents are usually prepared as an aqueous solution of 0.001% to 5%, and the aqueous solution is applied to the surface of a copper foil and then directly heated and dried. Further, the same effect can be obtained by using a coupling agent such as titanate-based or zirconate-based instead of the silane coupling agent.
(3) Production of copper-clad laminate
First, a copper foil surface (roughened surface) on which a thin copper foil is placed is laminated on a surface of an electrically insulating substrate made of glass epoxy resin, polyimide resin, or the like, and heated and pressed to produce a copper-clad laminate with or without a carrier. The surface-treated copper foil of the present invention has high tensile strength in a normal state and after heating, and therefore can be sufficiently used without a carrier. Next, the surface of the copper foil treated on the surface of the copper-clad laminate was irradiated with CO2Gas laser is used to open the holes. That is, CO was irradiated from the surface of the surface-treated copper foil on which the laser light absorbing layer was formed2The gas laser beam is used to perform a hole-forming process through the surface-treated copper foil and the resin substrate.
Examples
The present invention will be described in detail below with reference to examples.
(1) Production of copper foil and formation of laser light-absorbing layer
Electrolytic copper foils of examples 1 to 21 and comparative examples 1 to 9 were produced by the electrolytic solution, the current density, the cathode reduction step at the bath temperature shown in table 1 and the electrolytic deposition step based on the electrolytic conditions shown in table 2. These electrolytic copper foils were subjected to electrolytic plating treatment to form laser light absorbing layers in a plating bath having a composition shown in table 3, a treated surface, and electrolytic conditions (pulse width of pulse voltage, current density, time, bath temperature). In example 22, a laser light absorbing layer was formed by an alternating current, and in example 23, a laser light absorbing layer was formed by mecetcchbondcz-8000 treatment. Under the electrolysis conditions shown in table 3, Ion1 indicates the pulse current density in stage 1, Ion2 indicates the pulse current density in stage 2, ton1 indicates the pulse current application time in stage 1, ton2 indicates the pulse current application time in stage 2, and toff indicates the time when the current between the pulse current in stage 2 and the pulse current in stage 1 is 0. The laser light absorption layer was formed on the surface opposite to the roughened surface shown in table 4, and in examples 1 to 19, 22 to 23 and comparative examples 4, 6 to 8, the laser light absorption layer was formed on the M-plane (the S-plane was roughened), and in examples 20 and 21 and comparative example 9, the laser light absorption layer was formed on the S-plane (the M-plane was roughened). Comparative examples 1 to 3 and 5 did not have a laser light absorption layer formed.
[ Table 1]
(2) Roughening treatment
Next, a roughened layer having a fine uneven surface was formed on the surface opposite to the laser light absorption layer (roughened surface shown in table 4) by electrodeposition of roughened particles. In all examples and comparative examples, the roughening treatment layer was formed in the following order of roughening plating treatment.
(roughening plating treatment)
Copper sulfate: (calculated as copper concentration) 13g/L to 72g/L
Concentration of sulfuric acid: 26g/L to 133g/L
DL-malic acid: 0.1g/L to 5.0g/L
Liquid temperature: 18 ℃ to 67 DEG C
Current density: 3A/dm2To 67A/dm2
Treatment time: 1 second to 1 minute 55 seconds
(3) Formation of a nickel-containing base layer
In all of examples 1 to 23 and comparative examples 1 to 9, after the formation of the above-described roughened layer, electrolytic plating was performed on the roughened layer under the following nickel plating conditions to form a base layer (nickel deposition amount 0.06 mg/dm)2)。
< Nickel plating Condition >
Nickel sulfate: (calculated as nickel metal) 5.0g/L
Ammonium persulfate 40.0g/L
Boric acid 28.5g/L
Current density 1.5A/dm2
pH3.8
The temperature is 28.5 DEG C
For a period of 1 second to 2 minutes
(4) Formation of a zinc-containing heat-resistant treatment layer
In all of examples 1 to 23 and comparative examples 1 to 9, after the formation of the base layer, the base layer was subjected to electrolytic plating under the following zinc plating conditions to form a heat-resistant treatment layer (amount of zinc deposited: 0.05 mg/dm)2)。
< galvanizing Condition >
Zinc sulfate heptahydrate 1 g/L-30 g/L
10g/L to 300g/L of sodium hydroxide
Current density 0.1A/dm2To 10A/dm2
The temperature is 5 ℃ to 60 DEG C
For a period of 1 second to 2 minutes
(5) Formation of chromium-containing anticorrosive coating
In all of examples 1 to 23 and comparative examples 1 to 9, after the heat-resistant treatment layer was formed, a rust-preventive treatment layer was formed on the heat-resistant treatment layer by performing treatment under the following chromium plating treatment conditions (amount of chromium deposited: 0.02 mg/dm)2)。
< conditions of chromium plating >
(chromium plating bath)
Anhydrous chromic acid CrO3 2.5g/L
pH2.5
Current density 0.5A/dm2
The temperature is 15 ℃ to 45 DEG C
For a period of 1 second to 2 minutes
(6) Formation of silane coupling agent layer
In all of examples 1 to 23 and comparative examples 1 to 9, after the rust-preventive treatment layer was formed, a treatment liquid was applied to the rust-preventive treatment layer, the treatment liquid being obtained by adding methanol or ethanol to an aqueous solution of a silane coupling agent and adjusting the pH to a predetermined value. Then, after the retention for a predetermined period of time, the layer is dried with hot air, thereby forming a silane coupling agent layer.
(7) Evaluation method
< foil thickness >
The thickness of all the surface-treated copper foils of examples 1 to 23 and comparative examples 1 to 9 obtained by the above-described treatments (1) to (5) was measured as a mass thickness by an electronic balance. The results are shown in Table 1.
< tensile Strength >
The surface-treated copper foils of all of examples 1 to 23 and comparative examples 1 to 9 obtained by the above treatments (1) to (5) were cut into a size of 12.7mm × 130mm, and the tensile strength of the copper foil in a normal state was measured at room temperature by a model 1122 tensile tester testing apparatus from Instron. Further, a copper foil cut into 12.7 mm. times.130 mm was heated at 220 ℃ for 2 hours, then naturally cooled to room temperature, and the tensile strength after heating was measured in the same manner. The determination is according to IPC-TM-650. The results are shown in Table 4.
< expanded area ratio >
The surface shapes of all the surface-treated copper foils of examples 1 to 23 and comparative examples 1 to 9 obtained by the above-described treatments (1) to (5) were measured using WykoContourGT-K from BRUKER, and shape analysis was performed to determine the developed area ratio (Sdr). Shape analysis was performed by using a high-resolution CCD (charge coupled device) camera in a VSI (vertical scanning interference) measurement method under the conditions of a white light source, a measurement magnification of 10 times, a measurement range of 477 μm × 357.8 μm, a lateral sampling (larealsampling) of 0.38 μm, a speed (speed) of 1, a flyback (Backscan) of 5 μm, a Length (Length) of 5 μm, and a Threshold (Threshold) of 5%, and filtering processing for removing an item (termsemoval) was performed, followed by data processing. The results are shown in Table 4.
< Yxy color System >
In the Yxy color system of all the copper foils of examples 1 to 23 and comparative examples 1 to 9 obtained by the above-described treatments (1) to (5), Y, x, Y were measured by a colorimeter SM-T45(sugatest instruments ltd) using a 0 ° illumination light receiving at 45 ° and a 2 ° visual field (halogen lamp) of light source C. The results are shown in Table 4.
< pinhole >
All of the surface-treated copper foils of examples 1 to 23 and comparative examples 1 to 9 obtained by the above treatments (1) to (5) were cut into a size of 200mm × 200mm, and pinholes were marked by a light transmission method. Surface-treated copper foil 5 pieces (0.2 m in terms of gauge) having a size of 200mm × 200mm2) The diameter was confirmed by an optical microscope, and holes of 30 μm or more were counted as pinholes. The pinhole observed by an optical microscope includes a circular pinhole and an irregular pinhole, and the major axis of the pinhole (the distance between two points farthest apart from each other on the outer periphery of the pinhole) is measured as the diameter. Based on the obtained number of pinholes, the area per unit (m) was calculated2) Number of pinholes (number/m)2) The results are shown in Table 4.
< etching factor >
Next, a resist pattern having a line/space L & S of 100 μm/200 μm was formed by dry etching on all of the surface-treated copper foils of examples 1 to 23 and comparative examples 1 to 9 obtained by the above-described treatments (1) to (6) using a dry resist film. After etching of the wiring pattern using copper chloride and hydrochloric acid as an etching solution, the etching factor was measured. The etching factor (Ef) is a value represented by the following equation, where H represents the foil thickness of the surface-treated copper foil, B represents the bottom width of the formed wiring pattern, and T represents the top width of the formed wiring pattern.
Ef＝2H/(B-T)
If the etching factor is small, the vertical property of the side wall in the wiring pattern collapses, and in the case of a fine wiring pattern having a narrow line width, there is a risk of causing disconnection. In this example, the bottom width and the top width were measured with a microscope for a pattern at the time of etching (aligning the resist edge with the bottom of the copper foil pattern) at the proper position, and the etching factor was calculated. The results are shown in Table 4.
< laser numerical Aperture >
All of the surface-treated copper foil 2 sheets of examples 1 to 23 and comparative examples 1 to 9 obtained by the above treatment were bonded to both surfaces of the substrate FR4 by heating and pressing, thereby producing a CCL (copper clad laminate). Next, by CO2The laser drilling machine performs drilling processing of the laser beam emitted 100 times and counts the numerical aperture. The numerical apertures were shown in table 4 by irradiating the samples with the irradiation energy of 50W and 8W for a fixed irradiation time of 10 msec. Even when the irradiation energy was 8W, a sample having a small decrease in the numerical aperture was evaluated as a sample having high laser processability.
< operability: number of wrinkles defective >
The surface-treated copper foils of all examples 1 to 23 and comparative examples 1 to 9 obtained by the above-described treatments (1) to (5) were cut into a size of 200mm × 200mm, the surface-treated copper foils and the substrate FR4 were heated at 170 ℃ and 1.5MPa (pressure) for 1 hour to be pressure-bonded, 30 substrates were prepared, wrinkles were visually observed, and the number of wrinkles generated was counted as 1 number of wrinkles defective, whereby the number of wrinkles generated is shown in table 4. Thus, the surface-treated copper foil was evaluated for workability.
As is clear from table 4, in examples 1 to 23, the total tensile strength was 400MPa to 700MPa, the tensile strength after heating at 220 ℃ for 2 hours was 300MPa or more, the foil thickness was 7 μm or less, and the ratio of the developed area (Sdr) on the laser irradiated surface was 25% to 120%, and as shown by the evaluation results, the number of pinholes was 20 or less, Ef was 2.0 or more, the laser numerical aperture at 8W was 90 or more, the number of wrinkle defects was 3 or less, pinholes were few, laser processability was excellent, and workability was also excellent.
On the other hand, it is found that in comparative examples 1 to 9, the tensile strength is 400 to 700MPa, and the tensile strength after heating at 220 ℃ for 2 hours is 300MPa or more, but in comparative examples 2, 3, 5 to 7, and 9, the ratio of the developed area of the laser irradiated surface (Sdr) is not 25% to 120%, and therefore the laser numerical aperture at all 8W is less than 90, and the laser aperture opening property is poor. In comparative examples 1 and 4, it was found that the occurrence of pinholes exceeded 20 depending on the production conditions of the surface-treated copper foil, and comparative example 8 had poor laser-open property because the foil thickness was 9 μm.
Based on the above evaluation results, the relationship between the numerical aperture and the number of pinholes generated when the irradiation energy was 8W was shown in the graph of fig. 3 for the surface-treated copper foils of examples 1 to 21 and comparative examples 1 to 9. As is clear from fig. 3, the surface-treated copper foils of the examples had a large numerical aperture, and the occurrence of pinholes was small, and the laser processability was excellent, whereas the surface-treated copper foils of the comparative examples had a small numerical aperture, and the occurrence of pinholes was large, and the laser processability was poor.
Based on the above evaluation results, the relationship between the tensile strength in the normal state and the number of pinholes generated in the surface-treated copper foils of examples 1 to 21 and comparative examples 1 to 9 is shown in the graph of fig. 3. As is clear from fig. 3, the surface-treated copper foils of the examples had a large numerical aperture, and the occurrence of pinholes was small, and the laser processability was excellent, whereas the surface-treated copper foils of the comparative examples had a small numerical aperture, and the occurrence of pinholes was large, and the laser processability was poor.
Industrial applicability
According to the present invention, there can be provided a surface-treated copper foil which has high tensile strength, is excellent in etching properties, laser processability and workability of foil thinning, has few pinholes, and has high industrial applicability, with the line width or line width being reduced.
Description of the reference numerals
101, precipitating a copper foil; 102 rollers; 103 a polishing wheel device; 105 a cathode reduction unit; 106 electrolyte.
Claims (4)
1. A surface-treated copper foil for circuits which is processed by direct laser processing and has a tensile strength in the normal state of 400MPa to 700MPa, a tensile strength measured at ordinary temperature after heating at 220 ℃ for 2 hours of 300MPa or more, a foil thickness of 7 μm or less, an developed area ratio (Sdr) of at least one side of 25% to 120%, and a laser irradiation surface in a Yxy color system, Y having 25.0% to 65.5%, x having 0.30% to 0.48%, and Y having 0.28% to 0.41%.
2. The surface-treated copper foil for circuits according to claim 1,
the density of pinholes with diameter more than 30 μm is 20/m2The following.
3. The surface-treated copper foil for circuits according to claim 1,
the density of pinholes with diameter more than 30 μm is 10/m2The following.
4. A copper-clad laminate comprising the surface-treated copper foil for circuits of any one of claims 1 to 3, having an insulating substrate on the roughened layer side surface of the surface-treated copper foil.
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| JP2017068487 | 2017-03-30 | ||
| JP2017-068487 | 2017-03-30 | ||
| PCT/JP2018/011885 WO2018181061A1 (en) | 2017-03-30 | 2018-03-23 | Surface-treated copper foil and copper-clad laminate using same |
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| CN110475909B true CN110475909B (en) | 2021-12-24 |
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| JP (1) | JP6529684B2 (en) |
| KR (1) | KR102353878B1 (en) |
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| JP2019173164A (en) * | 2018-03-28 | 2019-10-10 | 日立金属株式会社 | Method of manufacturing aluminium foil |
| JP7247015B2 (en) * | 2019-05-08 | 2023-03-28 | 古河電気工業株式会社 | Electrolytic copper foil, surface-treated copper foil using the electrolytic copper foil, and copper-clad laminate and printed wiring board using the surface-treated copper foil |
| JP7270579B2 (en) * | 2019-06-19 | 2023-05-10 | 金居開發股▲分▼有限公司 | Micro-roughened electrodeposited copper foil and copper-clad laminate |
| CN111455416B (en) * | 2020-05-29 | 2021-02-09 | 佛冈建滔实业有限公司 | Preparation process of high-mechanical-property electrolytic copper foil of high-precision circuit board |
| CN115046367B (en) * | 2022-05-26 | 2024-04-09 | 九江德福科技股份有限公司 | Electrolytic copper foil surface drying treatment method and device |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1139415A1 (en) * | 2000-03-30 | 2001-10-04 | Nitto Denko Corporation | Water-permeable adhesive tape for semiconductor processing |
| JP2003340964A (en) * | 2002-03-18 | 2003-12-02 | Ube Ind Ltd | Copper-clad laminate board |
| JP2004237596A (en) * | 2003-02-06 | 2004-08-26 | Nippon Steel Chem Co Ltd | Flexible copper-clad laminated plate and its production method |
| JP2006022406A (en) * | 2000-09-22 | 2006-01-26 | Furukawa Circuit Foil Kk | Ultrathin copper foil with carrier |
| JP2006216194A (en) * | 2005-02-07 | 2006-08-17 | Toray Ind Inc | Magnetic recording medium support body and its manufacturing method |
| CN1985411A (en) * | 2004-02-11 | 2007-06-20 | 奥林公司 | Laser ablation resistant copper foil |
| CN101449633A (en) * | 2006-03-24 | 2009-06-03 | 宇部兴产株式会社 | Process for producing copper wiring polyimide film, and copper wiring polyimide film |
| JP2009172996A (en) * | 2007-12-26 | 2009-08-06 | Shin Etsu Chem Co Ltd | Flexible copper clad laminated board and its manufacturing method |
| CN101695215A (en) * | 2001-09-06 | 2010-04-14 | 奥林公司 | Copper foil with low profile bond enhancement |
| CN101787251A (en) * | 2010-02-10 | 2010-07-28 | 上海南亚覆铜箔板有限公司 | Bonding agent applicable to copper foil cladding laminated board with full light shading performance |
| JP2010236058A (en) * | 2009-03-31 | 2010-10-21 | Mitsui Mining & Smelting Co Ltd | Roughening-processed copper foil, method of manufacturing roughening-processed copper foil and copper clad laminate |
| CN101932439A (en) * | 2007-10-24 | 2010-12-29 | 宇部兴产株式会社 | Metal foil laminated polyimide resin substrate |
| CN103221583A (en) * | 2010-11-22 | 2013-07-24 | 三井金属矿业株式会社 | Surface treated copper foil |
| CN104717831A (en) * | 2013-11-29 | 2015-06-17 | Jx日矿日石金属株式会社 | Surface-treated copper foil, laminate, printed wiring board, electronic device, copper foil with carrier and method of manufacturing printed wiring board |
| CN105007687A (en) * | 2014-04-24 | 2015-10-28 | Jx日矿日石金属株式会社 | Copper foil with carrier, printed wiring board, laminated body, electronic machine and method for manufacturing printed wiring board |
| CN204820554U (en) * | 2015-07-30 | 2015-12-02 | 无锡光群雷射科技有限公司 | Holographic radium -shine case and bag packaging film of brand -new laser |
| CN105392297A (en) * | 2014-08-29 | 2016-03-09 | Jx日矿日石金属株式会社 | Method for manufacturing copper foil with carrier, method for manufacturing copper-clad laminate, method for manufacturing printed wiring board and method for manufacturing electronic device, and products thereof |
| CN105705329A (en) * | 2013-11-08 | 2016-06-22 | 日进材料股份有限公司 | Electrodeposited copper, and electrical component and battery comprising same |
| JP2017008410A (en) * | 2015-06-24 | 2017-01-12 | Ｊｘ金属株式会社 | Manufacturing method of copper foil with carrier, laminate and laminate, manufacturing method of printed wiring board and manufacturing method of electronic device |
| CN108044242A (en) * | 2017-12-18 | 2018-05-18 | 中国兵器装备集团自动化研究所 | A kind of device for laser machining copper foil hole |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006106956A1 (en) * | 2005-03-31 | 2006-10-12 | Mitsui Mining & Smelting Co., Ltd | Electrolytic copper foil and process for producing electrolytic copper foil, surface treated elctrolytic copper foil using said electrolytic copper foil, and copper-clad laminate plate and printed wiring board using said surface treated electrolytic copper foil |
| JP5653876B2 (en) | 2011-09-30 | 2015-01-14 | 古河電気工業株式会社 | Copper foil with laser absorbing layer, copper-clad laminate and printed wiring board using the copper foil |
| AU2013298673B2 (en) | 2012-07-31 | 2016-09-22 | Sanofi Sa | Arrangement for a drug delivery device |
| JP6425399B2 (en) | 2013-03-28 | 2018-11-21 | Ｊｘ金属株式会社 | Carrier-coated copper foil, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board |
-
2018
- 2018-03-23 WO PCT/JP2018/011885 patent/WO2018181061A1/en active Application Filing
- 2018-03-23 CN CN201880020021.6A patent/CN110475909B/en active Active
- 2018-03-23 JP JP2018545262A patent/JP6529684B2/en active Active
- 2018-03-23 KR KR1020197028362A patent/KR102353878B1/en active IP Right Grant
- 2018-03-28 TW TW107110690A patent/TWI693306B/en active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1139415A1 (en) * | 2000-03-30 | 2001-10-04 | Nitto Denko Corporation | Water-permeable adhesive tape for semiconductor processing |
| JP2006022406A (en) * | 2000-09-22 | 2006-01-26 | Furukawa Circuit Foil Kk | Ultrathin copper foil with carrier |
| CN101695215A (en) * | 2001-09-06 | 2010-04-14 | 奥林公司 | Copper foil with low profile bond enhancement |
| JP2003340964A (en) * | 2002-03-18 | 2003-12-02 | Ube Ind Ltd | Copper-clad laminate board |
| JP2004237596A (en) * | 2003-02-06 | 2004-08-26 | Nippon Steel Chem Co Ltd | Flexible copper-clad laminated plate and its production method |
| CN1985411A (en) * | 2004-02-11 | 2007-06-20 | 奥林公司 | Laser ablation resistant copper foil |
| JP2006216194A (en) * | 2005-02-07 | 2006-08-17 | Toray Ind Inc | Magnetic recording medium support body and its manufacturing method |
| CN101449633A (en) * | 2006-03-24 | 2009-06-03 | 宇部兴产株式会社 | Process for producing copper wiring polyimide film, and copper wiring polyimide film |
| CN101932439A (en) * | 2007-10-24 | 2010-12-29 | 宇部兴产株式会社 | Metal foil laminated polyimide resin substrate |
| JP2009172996A (en) * | 2007-12-26 | 2009-08-06 | Shin Etsu Chem Co Ltd | Flexible copper clad laminated board and its manufacturing method |
| JP2010236058A (en) * | 2009-03-31 | 2010-10-21 | Mitsui Mining & Smelting Co Ltd | Roughening-processed copper foil, method of manufacturing roughening-processed copper foil and copper clad laminate |
| CN101787251A (en) * | 2010-02-10 | 2010-07-28 | 上海南亚覆铜箔板有限公司 | Bonding agent applicable to copper foil cladding laminated board with full light shading performance |
| CN103221583A (en) * | 2010-11-22 | 2013-07-24 | 三井金属矿业株式会社 | Surface treated copper foil |
| CN105705329A (en) * | 2013-11-08 | 2016-06-22 | 日进材料股份有限公司 | Electrodeposited copper, and electrical component and battery comprising same |
| CN104717831A (en) * | 2013-11-29 | 2015-06-17 | Jx日矿日石金属株式会社 | Surface-treated copper foil, laminate, printed wiring board, electronic device, copper foil with carrier and method of manufacturing printed wiring board |
| CN105007687A (en) * | 2014-04-24 | 2015-10-28 | Jx日矿日石金属株式会社 | Copper foil with carrier, printed wiring board, laminated body, electronic machine and method for manufacturing printed wiring board |
| CN105392297A (en) * | 2014-08-29 | 2016-03-09 | Jx日矿日石金属株式会社 | Method for manufacturing copper foil with carrier, method for manufacturing copper-clad laminate, method for manufacturing printed wiring board and method for manufacturing electronic device, and products thereof |
| JP2017008410A (en) * | 2015-06-24 | 2017-01-12 | Ｊｘ金属株式会社 | Manufacturing method of copper foil with carrier, laminate and laminate, manufacturing method of printed wiring board and manufacturing method of electronic device |
| CN204820554U (en) * | 2015-07-30 | 2015-12-02 | 无锡光群雷射科技有限公司 | Holographic radium -shine case and bag packaging film of brand -new laser |
| CN108044242A (en) * | 2017-12-18 | 2018-05-18 | 中国兵器装备集团自动化研究所 | A kind of device for laser machining copper foil hole |
Non-Patent Citations (2)
| Title |
|---|
| "Experimental investigation on: laser shock micro-forming process using the mask and flexible pad";Xiao Wang 等;《Optics and Lasers in Engineering》;20170115;第88卷;第102-110页 * |
| "激光诱导精密沉积铜箔实验";黄志刚 等;《中国机械工程》;20161118(第22期);第2990-2994页 * |
Also Published As
| Publication number | Publication date |
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| KR20190133681A (en) | 2019-12-03 |
| TW201903212A (en) | 2019-01-16 |
| TWI693306B (en) | 2020-05-11 |
| CN110475909A (en) | 2019-11-19 |
| JPWO2018181061A1 (en) | 2019-04-04 |
| WO2018181061A1 (en) | 2018-10-04 |
| JP6529684B2 (en) | 2019-06-12 |
| KR102353878B1 (en) | 2022-01-19 |
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