WO2022244828A1 - 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 - Google Patents

粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 Download PDF

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Publication number
WO2022244828A1
WO2022244828A1 PCT/JP2022/020749 JP2022020749W WO2022244828A1 WO 2022244828 A1 WO2022244828 A1 WO 2022244828A1 JP 2022020749 W JP2022020749 W JP 2022020749W WO 2022244828 A1 WO2022244828 A1 WO 2022244828A1
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Prior art keywords
roughened
copper foil
particles
carrier
axis
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PCT/JP2022/020749
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English (en)
French (fr)
Japanese (ja)
Inventor
日山 沙織 小出
眞 細川
中川 美穂 栗原
知里 田坂
綾子 四井
田代 美智 溝口
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三井金属鉱業株式会社
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Priority to JP2023522712A priority Critical patent/JPWO2022244828A1/ja
Priority to KR1020237038695A priority patent/KR20240009937A/ko
Priority to CN202280036136.0A priority patent/CN117337344A/zh
Publication of WO2022244828A1 publication Critical patent/WO2022244828A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D5/16—Electroplating with layers of varying thickness
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed wiring board.
  • the MSAP method is a technique suitable for forming extremely fine circuits, and is carried out using a copper foil with a carrier in order to take advantage of its characteristics. For example, as shown in FIGS. 1 and 2, an ultra-thin copper foil (roughened copper foil 10) is placed on an insulating resin substrate 11 having a lower layer circuit 11b on a base substrate 11a, and a prepreg 12 and a primer layer 13 are formed thereon. (step (a)), peel off the carrier (not shown), and then form via holes 14 by laser drilling as necessary (step (b)).
  • step (c) After applying chemical copper plating 15 (step (c)), a predetermined pattern is masked by exposure and development using dry film 16 (step (d)), and electrolytic copper plating 17 is applied (step (e )).
  • step (e ) After the dry film 16 is removed to form the wiring portion 17a (step (f)), the unnecessary ultra-thin copper foil or the like between the mutually adjacent wiring portions 17a and 17a is removed by etching over the entire thickness thereof ( Step (g)), wiring 18 formed in a predetermined pattern is obtained.
  • Patent Document 1 International Publication No. 2016/117587
  • the average distance between surface peaks on the side of the release layer is 20 ⁇ m or less
  • the maximum height difference of the undulations on the side opposite to the release layer is A carrier-attached copper foil comprising an ultra-thin copper foil having a thickness of 1.0 ⁇ m or less
  • Patent Document 2 Japanese Patent Application Laid-Open No.
  • a carrier-attached copper foil having a ratio Sp/Spk to Spk of 3.271 or more and 10.739 or less is disclosed.
  • shear strength is one of the physical adhesion indices between a circuit and a substrate, and in order to effectively avoid the above-mentioned circuit peeling, a roughened copper foil suitable for improving the shear strength has been proposed. ing.
  • Patent Document 3 International Publication No.
  • a treated copper foil is disclosed. According to such a roughened copper foil, it is believed that both excellent etching properties and high shear strength can be achieved in the processing of copper-clad laminates or the manufacture of printed wiring boards.
  • a printed wiring board is provided with a copper foil processed into a wiring pattern and an insulating resin base material. Transmission loss consists of conductor loss caused by the copper foil and dielectric loss caused by the insulating resin base material.
  • Patent Document 4 Japanese Patent No. 6462961 describes a surface-treated copper foil in which a roughening treatment layer, an anti-corrosion treatment layer and a silane coupling layer are laminated in this order on at least one side of the copper foil.
  • the interface developed area ratio Sdr measured from the surface of the coupling layer is 8% or more and 140% or less, the root mean square surface gradient Sdq is 25° or more and 70° or less, and the surface texture aspect ratio Str is 0.25 or more and 0. 0.79 or less. It is said that such a surface-treated copper foil makes it possible to manufacture a printed wiring board with little transmission loss of high-frequency electrical signals and excellent adhesion during reflow soldering.
  • copper foil with low transmission loss that is, copper foil with excellent high-frequency characteristics
  • transmission loss can be suppressed by smoothing the copper foil and miniaturizing the roughened particles, the physical adhesion (particularly shear strength) between the copper foil and the substrate resin will decrease. .
  • the present inventors have recently found that in a roughened copper foil, by giving a surface profile in which the average height of roughened particles and the proportion of spherical particles in the roughened particles are controlled within predetermined ranges, The present inventors have found that both excellent transmission characteristics and high shear strength can be achieved in the processing of copper-clad laminates or the manufacture of printed wiring boards.
  • an object of the present invention is to provide a roughened copper foil that can achieve both excellent transmission characteristics and high shear strength in the processing of copper-clad laminates or the manufacture of printed wiring boards.
  • the average height of the roughened particles is 70 nm or less, and the plurality of roughened particles occupy The proportion of the spherical particles is 30% or more
  • the spherical particles have a long axis, a middle axis and a short axis that are orthogonal to each other with respect to the roughened particles, and when the length L of the long axis is 1.0, the length M of the middle axis is A roughened copper foil, which is a particle that satisfies 0.3 ⁇ M ⁇ 1.0 and the minor axis length S satisfies 0.3 ⁇ S ⁇ 1.0.
  • the base area ratio is the ratio of the projected area to the base area of each roughened particle, and the base area is defined as the xy plane area value of the voxel that constitutes the bottom surface of each roughened particle, and the projected The roughening treatment according to any one of aspects 1 to 3, wherein the area is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction in each roughening particle.
  • Copper foil [Aspect 5] The roughened copper foil according to aspect 4, wherein the average value of the bottom area ratio is 2.0 or more and 3.0 or less.
  • Aspect 6 The roughened copper foil according to any one of aspects 1 to 5, further comprising an anticorrosive layer and/or a silane coupling agent layer on the roughened surface.
  • a copper clad laminate comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
  • a printed wiring board comprising the roughened copper foil according to any one of aspects 1 to 6 or the carrier-attached copper foil according to aspect 7.
  • FIG. 2 is a flow chart of the steps for explaining the MSAP method, showing the first half of the steps (steps (a) to (d)).
  • FIG. 2 is a flow chart of the steps for explaining the MSAP method, showing the latter half of the steps (steps (e) to (g)).
  • FIG. 4 is a schematic diagram of a roughening particle divided into a plurality of voxels, and is a diagram for explaining a projected area and a bottom area;
  • FIG. 4 is a diagram showing regions where laser light cannot enter when a roughened surface is measured with a laser microscope.
  • 3 is a diagram showing x-, y-, and z-axes in 3D-SEM observation, and a slice plane S in relation to a roughened copper foil.
  • FIG. FIG. 4 is a diagram showing the relationship between each axis after rotating the x-axis, y-axis, and z-axis and the roughened copper foil in 3D-SEM image analysis.
  • image obtained using FIB-SEM on the roughened surface refers to cross-sectional processing by FIB (focused ion beam) on the roughened surface of the roughened copper foil. It means an aggregate of cross-sectional images acquired through cross-sectional observation by a SEM (scanning electron microscope), and constitutes three-dimensional shape data as a whole. Specifically, as shown in FIG. 5, the x-axis and z-axis are defined as the in-plane directions of the roughened copper foil 10, and the y-axis is defined as the thickness direction of the roughened copper foil 10.
  • a cross-sectional image including the roughened surface of the roughened copper foil 10 on the slice plane S parallel to the xy plane is acquired, and this slice plane is translated by a predetermined interval (for example, 5 nm) in the z-axis direction. It is an aggregate of cross-sectional images obtained in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above) while the surface is being processed.
  • the “average height of roughened particles” means the average height of roughened particles present in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed in plan). means value.
  • the average height of the roughened particles can be specified by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface. In the three-dimensional image analysis, the underlying shape of the copper foil before roughening may be determined as roughening particles (convex portions). Even if they are not formed by
  • the term “spherical particles” refers to roughened particles having a long axis, a middle axis, and a short axis that are perpendicular to each other, and when the length L of the long axis is 1.0, the length of the middle axis It means a particle in which the length M satisfies 0.3 ⁇ M ⁇ 1.0 and the minor axis length S satisfies 0.3 ⁇ S ⁇ 1.0.
  • the term “flat particles” means that the length M of the middle axis satisfies 0.3 ⁇ M ⁇ 1.0 when the length L of the long axis is 1.0, and the It means a particle having a short axis length S satisfying S ⁇ 0.3.
  • the term “elongated particles” means that the length M of the middle axis satisfies M ⁇ 0.3 when the length L of the long axis is 1.0, and the length of the short axis We mean particles whose height S satisfies S ⁇ 0.3.
  • the term “proportion of spherical particles” means the ratio of spherical particles to the roughened particles present in a predetermined analysis area (for example, an area of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above). do.
  • the number NS of spherical particles divided by the sum of the numbers of each particle (that is, the sum of the number NS of spherical particles, the number NF of flat particles, and the number NE of elongated particles) is multiplied by 100.
  • Classification of spherical particles, flat particles and elongated particles can be performed by three-dimensional image analysis of images obtained using FIB-SEM on the roughened surface.
  • the “average value of the bottom area ratio” means the average of the bottom area ratios of the roughened particles present in a predetermined analysis area (for example, a region of 2400 nm ⁇ 2400 nm when the roughened surface is viewed from above).
  • value, and “base area ratio” means the ratio of the projected area to the base area for each roughening particle.
  • the base area and projected area can be determined by dividing the roughening particle into voxels. Specifically, as shown in FIG.
  • the projected area P is defined as the product of the x value of the maximum voxel in the x-axis direction and the y value of the maximum voxel in the y-axis direction of the roughening particles 10a.
  • the bottom area B is defined as the xy plane area value of the voxels forming the bottom surface of the roughening particle 10a.
  • the average height of roughened particles, the ratio of spherical particles, and the average value of the base area ratio are obtained by three-dimensional image analysis of the image obtained using FIB-SEM for the roughened surface.
  • Such three-dimensional image analysis can be performed using commercially available software.
  • the three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (manufactured by Nippon Visual Science Co., Ltd.
  • electrode surface of the carrier refers to the surface that was in contact with the cathode when the carrier was produced.
  • the "deposition surface" of the carrier refers to the surface on which electrolytic copper is deposited during carrier production, that is, the surface that is not in contact with the cathode.
  • the copper foil according to the present invention is a roughened copper foil.
  • This roughened copper foil has a roughened surface on at least one side.
  • the roughened surface has a plurality of roughened particles including spherical particles. Then, when an image obtained by using an FIB-SEM on the roughened surface is subjected to three-dimensional image analysis, the average height of the roughened particles is 70 nm or less. Moreover, the ratio of the spherical particles to the plurality of roughened particles is 30% or more.
  • the copper clad laminate in the roughened copper foil, by imparting a surface profile in which the average height of the roughened particles and the proportion of spherical particles in the roughened particles are controlled within a predetermined range, the copper clad laminate can be obtained.
  • the roughened copper foil of the present invention unexpectedly makes it possible to achieve both.
  • the mechanism is not necessarily clear, one of the factors is as follows. First, by reducing the average height of the roughened particles to 70 nm or less, it is possible to reduce the transmission loss by miniaturizing the roughened particles. As the roughened particles become finer, there is concern that the shear strength will decrease. By increasing the proportion of spherical particles in the roughened particles to 30% or more, the anchor effect based on the constricted shape of the spherical particles is exhibited. It is considered that the fine particles can achieve excellent adhesion to the resin.
  • FIG. 4 schematically shows an example of measurement of the roughened surface using a laser microscope.
  • a laser beam is irradiated from above the roughened surface.
  • the average height of the roughened particles is 70 nm or less, preferably 20 nm or more and 70 nm or less, more preferably 30 nm or more and 70 nm or less, even more preferably 50 nm or more and 70 nm or less, and particularly preferably 60 nm or more and 70 nm or less. By doing so, it is possible to achieve excellent transmission characteristics while maintaining high shear strength.
  • the proportion of spherical particles in the roughened particles is 30% or more, preferably 30% or more and 90% or less, more preferably 30% or more and 70% or less, still more preferably 30% or more and 50% or less, particularly preferably 35%. 45% or less. By doing so, it is possible to achieve high shear strength while having excellent transmission characteristics.
  • the average value of the bottom area ratio of the roughened particles is preferably 3.0 or less, more preferably 2.0 or more and 3.0 or less.
  • the mechanism by which the etchability is improved by controlling the average value of the bottom area ratio is not necessarily clear, one of the factors is as follows. That is, when forming a circuit on a copper-clad laminate or the like by etching, it is necessary to remove not only the copper foil on the surface but also the roughened particles that have penetrated into the substrate resin. At this time, since the constricted portion of the roughening particles is too thin, it becomes difficult for the etchant to penetrate into the portion of the resin substrate in which the roughening particles have been bitten, and a large amount of etching is required to eliminate the residual copper. things can happen.
  • the roughened particles will have a constricted shape that is convenient for the penetration of the etchant, and the amount of etching required to remove the roughened particles will be reduced. can be reduced.
  • the thickness of the roughened copper foil is not particularly limited, it is preferably 0.1 ⁇ m or more and 35 ⁇ m or less, more preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less, and still more preferably 1.0 ⁇ m or more and 3.0 ⁇ m or less.
  • the roughened copper foil is not limited to a general copper foil whose surface has been roughened, and may be a carrier-attached copper foil whose copper foil surface has been roughened.
  • the thickness of the roughened copper foil is the thickness not including the height of the roughened particles formed on the surface of the roughened surface (thickness of the copper foil itself constituting the roughened copper foil). is.
  • a copper foil having a thickness within the above range is sometimes called an ultra-thin copper foil.
  • the roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have roughened surfaces on both sides, or may have a roughened surface only on one side. It is preferable that the roughened surface comprises a plurality of roughening particles, and each of the plurality of roughening particles consists of copper particles.
  • the copper particles may consist of metallic copper, or may consist of a copper alloy.
  • the roughening treatment for forming the roughened surface can be preferably carried out by forming roughening particles with copper or a copper alloy on the copper foil.
  • This roughening treatment is preferably carried out according to a plating technique involving three stages of plating processes.
  • a copper sulfate solution having a copper concentration of 5 g/L or more and 15 g/L or less and a sulfuric acid concentration of 200 g/L or more and 250 g/L or less is used, and the liquid temperature is 25° C. or more and 45° C. or less.
  • Electrodeposition is preferably carried out under the plating conditions of a current density of 2 A/dm 2 or more and 4 A/dm 2 or less.
  • the first-stage plating process is preferably performed twice in total using two tanks.
  • a copper sulfate solution with a copper concentration of 60 g/L or more and 80 g/L or less and a sulfuric acid concentration of 200 g/L or more and 260 g/L or less was used, and the liquid temperature was 45 ° C. or more and 55 ° C. or less, and the current density was 10 A. /dm 2 or more and 15 A/dm 2 or less.
  • the copper concentration is 5 g/L or more and 20 g/L or less
  • the sulfuric acid concentration is 60 g/L or more and 90 g/L or less
  • the chlorine concentration is 20 mg/L or more and 40 mg/L or less
  • the 9-phenylacridine (9PA) concentration is preferably performed using a copper sulfate solution of 100 mg/L or more and 200 mg/L or less under plating conditions of a liquid temperature of 25° C. or more and 35° C. or less and a current density of 30 A/dm 2 or more and 60 A/dm 2 or less.
  • Each of the second and third plating steps may be performed twice in total using two baths, but is preferably completed in one time. Through such a plating process, it becomes easier to form bumps on the treated surface that are convenient for satisfying the surface parameters described above.
  • the roughened copper foil may be subjected to antirust treatment and may have an antirust treatment layer formed thereon.
  • the antirust treatment preferably includes plating with zinc.
  • the plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment.
  • the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, Co and Mo.
  • the Ni/Zn adhesion ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, and still more preferably 2.7 to 4 in mass ratio.
  • the rust prevention treatment preferably further includes chromate treatment, and this chromate treatment is more preferably performed on the surface of the plating containing zinc after the plating treatment using zinc.
  • a particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment and subsequent chromate treatment.
  • the surface of the roughened copper foil may be treated with a silane coupling agent to form a silane coupling agent layer.
  • a silane coupling agent layer can be formed by appropriately diluting the silane coupling agent, coating it, and drying it.
  • silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.
  • epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)but
  • amino-functional silane coupling agents or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or 3-methacrylic Acrylic functional silane coupling agents such as roxypropyltrimethoxysilane, or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, and the like.
  • the roughened copper foil preferably further comprises an antirust treatment layer and/or a silane coupling agent layer on the roughened surface, more preferably the antirust treatment layer and the silane coupling agent layer.
  • an antirust treatment layer and/or a silane coupling agent layer on the roughened surface, more preferably the antirust treatment layer and the silane coupling agent layer.
  • the numerical value means a numerical value obtained by measuring and analyzing the roughened copper foil after the antirust treatment layer and/or the silane coupling agent treatment layer has been formed.
  • the antirust layer and the silane coupling agent layer may be formed not only on the roughened surface side of the roughened copper foil, but also on the side where the roughened surface is not formed.
  • the roughened copper foil of the present invention may be provided in the form of a carrier-attached copper foil.
  • a carrier By adopting the form of a copper foil with a carrier, it is possible to realize excellent laser workability and fine line circuit formability. That is, according to a preferred embodiment of the present invention, a carrier, a release layer provided on the carrier, and the roughened copper foil provided on the release layer with the roughened surface facing outward, A copper foil with carrier is provided.
  • a known layer structure can be employed, except for using the roughened copper foil of the present invention.
  • a carrier is a support for supporting the roughened copper foil to improve its handling properties
  • a typical carrier includes a metal layer.
  • Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, resin film or glass whose surface is metal-coated with copper or the like, and copper foil is preferred.
  • the copper foil may be a rolled copper foil or an electrolytic copper foil, preferably an electrolytic copper foil.
  • the thickness of the carrier is typically 250 ⁇ m or less, preferably 7 ⁇ m or more and 200 ⁇ m or less.
  • the surface of the carrier on the release layer side is preferably smooth. That is, in the manufacturing process of the carrier-attached copper foil, an ultra-thin copper foil (before roughening treatment) is formed on the release layer side surface of the carrier.
  • the roughened copper foil of the present invention is used in the form of a carrier-attached copper foil, the roughened copper foil can be obtained by roughening such an ultra-thin copper foil. Therefore, by smoothing the surface of the carrier on the release layer side, the outer surface of the ultra-thin copper foil can also be smoothed. It becomes easy to realize a roughened surface having an average height of roughened particles within the above-described predetermined range.
  • the surface of the carrier on the release layer side can be smoothed, for example, by polishing the surface of the cathode used in electrolytic foil production of the carrier with a buff of a predetermined number to adjust the surface roughness. That is, the surface profile of the cathode adjusted in this way is transferred to the electrode surface of the carrier, and an ultra-thin copper foil is formed on the electrode surface of the carrier with a release layer interposed therebetween. It is possible to impart a smooth surface condition that facilitates the realization of the roughened surface described above.
  • the buff number is preferably #2000 or more and #3000 or less, more preferably #2000 or more and #2500 or less.
  • the electrode surface of the carrier obtained by using the cathode polished with a buff of #2000 or more and #2500 or less has a slight undulation compared to the smooth foil deposition surface, so it is possible to ensure adhesion and smoothness. , it is possible to achieve a good balance between high adhesion and excellent transmission characteristics.
  • electrolytic foil manufacturing was performed using an electrolytic solution containing additives.
  • the carrier deposition surface side may be the surface of the carrier on the peeling layer side.
  • the release layer is a layer that has the function of weakening the peeling strength of the carrier, ensuring the stability of the strength, and suppressing interdiffusion that may occur between the carrier and the copper foil during press molding at high temperatures. .
  • the release layer is generally formed on one side of the carrier, but may be formed on both sides.
  • the release layer may be either an organic release layer or an inorganic release layer.
  • organic components used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like.
  • Examples of the nitrogen-containing organic compound include triazole compounds, imidazole compounds, etc. Among them, triazole compounds are preferable in terms of easily stabilizing peelability.
  • triazole compounds examples include 1,2,3-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole, 3-amino- 1H-1,2,4-triazole and the like.
  • sulfur-containing organic compounds examples include mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, and the like.
  • carboxylic acids include monocarboxylic acids, dicarboxylic acids, and the like.
  • examples of inorganic components used for the inorganic release layer include Ni, Mo, Co, Cr, Fe, Ti, W, P, Zn, chromate treatment films, and the like.
  • the release layer may be formed by contacting at least one surface of the carrier with a release layer component-containing solution to fix the release layer component on the surface of the carrier.
  • this contact may be performed by immersion in the release layer component-containing solution, spraying the release layer component-containing solution, or flowing the release layer component-containing solution.
  • Fixing of the release layer component to the carrier surface may be carried out by adsorption or drying of the release layer component-containing solution, electrodeposition of the release layer component in the release layer component-containing solution, or the like.
  • the thickness of the release layer is typically 1 nm or more and 1 ⁇ m or less, preferably 5 nm or more and 500 nm or less.
  • another functional layer may be provided between the release layer and the carrier and/or the roughened copper foil.
  • auxiliary metal layers include auxiliary metal layers.
  • the auxiliary metal layer preferably consists of nickel and/or cobalt. By forming such an auxiliary metal layer on the surface side of the carrier and/or on the surface side of the roughened copper foil, during hot press molding at high temperature or for a long time, it may occur between the carrier and the roughened copper foil. Mutual diffusion can be suppressed and the stability of carrier peeling strength can be ensured.
  • the thickness of the auxiliary metal layer is preferably 0.001 ⁇ m or more and 3 ⁇ m or less.
  • the roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil or the carrier-attached copper foil.
  • a copper-clad laminate comprising the roughened copper foil or the carrier-attached copper foil.
  • This copper-clad laminate comprises the roughened copper foil of the present invention and a resin layer provided in close contact with the roughened surface of the roughened copper foil.
  • the roughened copper foil may be provided on one side of the resin layer, or may be provided on both sides.
  • the resin layer comprises resin, preferably insulating resin.
  • the resin layer is preferably prepreg and/or resin sheet.
  • Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper.
  • Preferred examples of insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins.
  • Examples of the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
  • the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation.
  • the thickness of the resin layer is not particularly limited, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 2 ⁇ m or more and 400 ⁇ m or less, and still more preferably 3 ⁇ m or more and 200 ⁇ m or less.
  • the resin layer may be composed of multiple layers. A resin layer such as a prepreg and/or a resin sheet may be provided on the roughened copper foil in advance via a primer resin layer that is applied to the surface of the copper foil.
  • the roughened copper foil of the present invention is preferably used for producing a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board comprising the roughened copper foil or the carrier-attached copper foil.
  • a printed wiring board comprising the roughened copper foil or the carrier-attached copper foil.
  • the printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated.
  • the copper layer is a layer derived from the roughened copper foil of the present invention.
  • the resin layer is as described above for the copper-clad laminate.
  • the printed wiring board can employ a known layer structure except for using the roughened copper foil of the present invention.
  • Specific examples of printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the roughened copper foil of the present invention to one or both sides of a prepreg to form a cured laminate, and then forming a circuit on the printed wiring board.
  • a multilayer printed wiring board etc. are mentioned.
  • other specific examples include flexible printed wiring boards, COF, TAB tapes, etc., in which the roughened copper foil of the present invention is formed on a resin film to form a circuit.
  • a resin-coated copper foil is formed by applying the above resin layer to the roughened copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above printed circuit board.
  • the roughened copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive (MSAP) method, the subtractive method, etc.
  • MSAP modified semi-additive
  • the build-up wiring board and the roughened copper foil are removed.
  • More advanced specific examples include antenna elements in which the resin-coated copper foil is laminated on a base material to form a circuit, and electronic materials and windows for panels and displays in which a pattern is formed by laminating the resin-coated copper foil on glass or a resin film via an adhesive layer.
  • An electronic material for glass, an electromagnetic wave shielding film obtained by applying a conductive adhesive to the roughened copper foil of the present invention, and the like are also included.
  • the printed wiring board provided with the roughened copper foil of the present invention is used in applications such as automobile antennas, mobile phone base station antennas, high-performance servers, collision prevention radars, etc., which are used in high frequency bands with signal frequencies of 10 GHz or higher. It is suitably used as a high-frequency substrate to be used.
  • the roughened copper foil of the present invention is suitable for the MSAP method. For example, when the circuit is formed by the MSAP method, the configurations shown in FIGS. 1 and 2 can be adopted.
  • Examples 1-3 A copper foil with a carrier provided with a roughened copper foil was produced as follows.
  • the carrier on which the organic release layer was formed was immersed in a solution containing nickel concentration of 20 g/L prepared using nickel sulfate, and the liquid temperature was 45° C., pH 3, current density 5 A/L. Under conditions of dm 2 , a deposition amount of nickel equivalent to a thickness of 0.001 ⁇ m was deposited onto the organic release layer. Thus, a nickel layer was formed as an auxiliary metal layer on the organic release layer.
  • the surface of the ultra-thin copper foil thus formed was subjected to a roughening treatment to form a roughened copper foil, thereby obtaining a carrier-attached copper foil.
  • a roughening treatment in Examples 1 and 2, the following three stages of roughening treatment were performed.
  • the roughening treatment in the first step was carried out in two steps. Specifically, using an acidic copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1, the roughening treatment was performed twice at the current density and liquid temperature shown in Table 1.
  • the acid copper sulfate solution having the copper concentration and sulfuric acid concentration shown in Table 1 was used, and the roughening treatment was performed at the current density and liquid temperature shown in Table 1.
  • the third stage roughening treatment uses an acidic copper sulfate solution with the copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9PA) concentration shown in Table 1, and the current density and liquid temperature shown in Table 1 was subjected to roughening treatment.
  • Example 3 a two-step roughening treatment was performed.
  • This two-stage roughening treatment consists of a baking plating process for depositing fine copper grains on an ultra-thin copper foil and a covering plating process for preventing the fine copper grains from falling off.
  • carboxybenzotriazole (CBTA) was added to an acidic copper sulfate solution with a copper concentration of 10 g / L and a sulfuric acid concentration of 200 g / L so that the concentration shown in Table 1 was obtained, and the current density shown in Table 1 was obtained.
  • the roughening treatment was performed at liquid temperature.
  • electrodeposition was performed under smooth plating conditions of a liquid temperature of 52° C. and a current density shown in Table 1 using an acidic copper sulfate solution with a copper concentration of 70 g/L and a sulfuric acid concentration of 240 g/L.
  • the roughened surface of the obtained copper foil with carrier was subjected to antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
  • antirust treatment comprising zinc-nickel alloy plating treatment and chromate treatment.
  • the roughening treatment layer and the carrier A zinc-nickel alloy plating treatment was performed on the surface of the Next, the zinc-nickel alloy plated surface was subjected to chromate treatment using an aqueous solution containing 1 g/L of chromic acid under the conditions of pH 12 and current density 1 A/dm 2 .
  • Silane coupling agent treatment An aqueous solution containing a commercially available silane coupling agent is adsorbed on the surface of the roughened copper foil side of the carrier-attached copper foil, and the water is evaporated with an electric heater to perform the silane coupling agent treatment. did At this time, the carrier side was not treated with the silane coupling agent.
  • Example 4 (Comparison) A roughened copper foil was produced in the same manner as in Example 1 except for the following a) and b). a) Instead of the carrier-attached copper foil, the deposition surface of the following electrolytic copper foil was subjected to a roughening treatment. b) The roughening treatment conditions were changed as shown in Table 1.
  • Example 5 (Comparison) A carrier-attached copper foil was produced in the same manner as in Example 1, except that the ultra-thin copper foil was not subjected to roughening treatment.
  • the roughened copper foils or carrier-attached copper foils produced in Evaluation Examples 1 to 5 were subjected to various evaluations shown below.
  • each convex part is a spherical particle , flat particles, and elongated particles. Convex portions whose shape cannot be determined (calculation of S, M, and L) due to reasons such as a small number of pixels are excluded from the calculation as noise.
  • the results were as shown in Table 3.
  • ⁇ Average value of bottom area ratio The numerical value of “surface_voxels (voxels)” in each convex portion was defined as the xy plane area value (that is, the bottom area) of the voxels forming the bottom surface of each roughening particle. Also, the numerical value of "size_X (voxels)" in each convex portion is the x value of the maximum voxel in the x-axis direction for each roughening particle, and the numerical value of "size_Y (voxels)” is the y value of the maximum voxel in the y-axis direction. did. Then, the product of the x value and the y value was defined as the projected area of each roughening particle. The ratio of the projected area to the bottom area of each roughening particle was determined as the bottom area ratio, and the average value was calculated. The results were as shown in Table 3.
  • a dry film was attached to the laminate for evaluation described above, and exposure and development were performed. After depositing a copper layer by pattern plating on the laminate masked with the developed dry film, the dry film was peeled off. The exposed copper portion was etched with a sulfuric acid-hydrogen peroxide-based etchant to prepare a sample for shear strength measurement having a height of 15 ⁇ m, a width of 14 ⁇ m, and a length of 150 ⁇ m. Using a bonding strength tester (4000Plus Bondtester manufactured by Nordson DAGE), the shear strength when the sample for shear strength measurement was pushed down from the side was measured.
  • a bonding strength tester 4000Plus Bondtester manufactured by Nordson DAGE
  • the test type was a destructive test, and the measurement was performed under the conditions of a test height of 5 ⁇ m, a descending speed of 0.05 mm/s, a test speed of 200 ⁇ m/s, a tool movement of 0.03 mm, and a rupture recognition point of 10%.
  • the obtained shear strength was rated and evaluated according to the following criteria, and evaluations A and B were judged to be acceptable. The results were as shown in Table 2.
  • circuit formability evaluation of etching property
  • a laminate for evaluation was produced in the same procedure as for the shear strength. This laminate for evaluation was etched with a sulfuric acid-hydrogen peroxide-based etchant by 0.2 ⁇ m. Measurements were made by checking with an optical microscope (500x) after each etching. When the etching progresses and the laminate for evaluation is observed with an optical microscope, the starting point is when the base resin begins to be observed, and the end point is when the copper (including roughening particles) on the surface is completely removed. did. The etching amount (depth) required from the start point to the end point was defined as the etching amount of the roughening particles.
  • the etching amount of the roughened particles is 0.4 ⁇ m
  • the etching amount of the obtained roughening particles was graded and evaluated according to the following criteria. The results were as shown in Table 3.

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PCT/JP2022/020749 2021-05-20 2022-05-18 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板 WO2022244828A1 (ja)

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Citations (4)

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JP2014152352A (ja) * 2013-02-06 2014-08-25 Sh Copper Products Corp 複合銅箔および複合銅箔の製造方法
JP2016089192A (ja) * 2014-10-30 2016-05-23 株式会社Ｓｈカッパープロダクツ 表面処理銅箔及び積層板
WO2017099094A1 (ja) * 2015-12-09 2017-06-15 古河電気工業株式会社 プリント配線板用表面処理銅箔、プリント配線板用銅張積層板及びプリント配線板
WO2018211951A1 (ja) * 2017-05-19 2018-11-22 三井金属鉱業株式会社 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板

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WO2016117587A1 (ja) 2015-01-22 2016-07-28 三井金属鉱業株式会社 キャリア付極薄銅箔及びその製造方法
MY186266A (en) * 2015-03-31 2021-07-01 Mitsui Mining & Smelting Co Ltd Roughened copper foil, copper foil provided with carrier, copper-clad laminated sheet, and printed wiring board
JP6200042B2 (ja) 2015-08-06 2017-09-20 Ｊｘ金属株式会社 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
JP6905157B2 (ja) 2018-08-10 2021-07-21 三井金属鉱業株式会社 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014152352A (ja) * 2013-02-06 2014-08-25 Sh Copper Products Corp 複合銅箔および複合銅箔の製造方法
JP2016089192A (ja) * 2014-10-30 2016-05-23 株式会社Ｓｈカッパープロダクツ 表面処理銅箔及び積層板
WO2017099094A1 (ja) * 2015-12-09 2017-06-15 古河電気工業株式会社 プリント配線板用表面処理銅箔、プリント配線板用銅張積層板及びプリント配線板
WO2018211951A1 (ja) * 2017-05-19 2018-11-22 三井金属鉱業株式会社 粗化処理銅箔、キャリア付銅箔、銅張積層板及びプリント配線板

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