WO2015151935A1 - キャリア箔付銅箔、銅張積層板及びプリント配線板 - Google Patents
キャリア箔付銅箔、銅張積層板及びプリント配線板 Download PDFInfo
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- WO2015151935A1 WO2015151935A1 PCT/JP2015/058928 JP2015058928W WO2015151935A1 WO 2015151935 A1 WO2015151935 A1 WO 2015151935A1 JP 2015058928 W JP2015058928 W JP 2015058928W WO 2015151935 A1 WO2015151935 A1 WO 2015151935A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/18—Working by laser beam, e.g. welding, cutting or boring using absorbing layers on the workpiece, e.g. for marking or protecting purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
- B23K26/382—Removing material by boring or cutting by boring
- B23K26/389—Removing material by boring or cutting by boring of fluid openings, e.g. nozzles, jets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
- B23K2101/40—Semiconductor devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/16—Composite materials, e.g. fibre reinforced
- B23K2103/166—Multilayered materials
- B23K2103/172—Multilayered materials wherein at least one of the layers is non-metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0315—Oxidising metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
- H05K3/0035—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material of blind holes, i.e. having a metal layer at the bottom
Definitions
- This application relates to copper foil with carrier foil, copper clad laminate and printed wiring board.
- the multilayer printed wiring board includes a plurality of conductor layers, and the conductor layers are electrically connected to each other by interlayer conduction means such as through holes.
- interlayer conduction means such as through holes.
- via holes have been used as interlayer conduction means instead of through holes in order to cope with higher density mounting and finer wiring.
- the through hole is generally formed by drilling, whereas the via hole is formed by laser processing. Therefore, the via hole has a smaller diameter compared to the through hole, which is advantageous for high-density mounting.
- various forms such as a blind via hole (BVH), an interstitial via hole (IVH), a stacking via hole and the like are known.
- Patent Document 1 discloses that in the method of manufacturing a double-sided printed wiring board that requires interlayer conductive copper plating such as a through hole or a via hole or a multilayer printed wiring board having three or more layers, the print Copper foil with a peelable type carrier foil is used for the copper foil located on the outer layer of the wiring board, and the necessary processing of the through hole for the through hole or the hole for the via hole is performed without peeling off the carrier foil.
- the double-sided printing is characterized in that the outer layer circuit pattern is registered on the copper foil located in the outer layer and then etched. Preparation method for one-plate or three or more layers of the multilayer printed wiring board. "Is disclosed.
- Patent Document 1 a material excellent in laser drilling performance when performing drilling from the carrier foil surface of the copper foil with carrier foil in the outer layer of the multilayer laminate using a carbon dioxide laser is desired. Has been.
- the copper foil with a carrier foil is a copper foil with a carrier foil having a layer configuration of carrier foil / peeling layer / bulk copper layer, and is composed of a copper composite compound on both sides of the copper foil with a carrier foil.
- a roughening treatment layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a length of 500 nm or less is provided, and the roughening treatment layer provided on the surface of the carrier foil is used as a laser light absorption layer.
- the roughening treatment layer used on the surface of the bulk copper layer is used as an adhesive layer with the insulating layer constituting material.
- the copper clad laminate according to the present application is characterized in that the adhesive layer side of the bulk copper layer of the copper foil with carrier foil according to the present application is laminated on at least one surface of the insulating layer constituting material.
- the printed wiring board according to the present application is formed using the bulk copper layer of the copper foil with carrier foil according to the present application.
- the copper foil with carrier foil has a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound on both surfaces of the copper foil with carrier foil.
- the roughening process layer which has is provided.
- the roughening treatment layer provided on the surface of the carrier foil is used as a laser light absorption layer, and the roughening treatment layer provided on the surface of the bulk copper layer is used as an adhesive layer with the insulating layer constituting material.
- the maximum length of the copper composite compound is formed by needle-like or plate-like convex portions having a length of 500 nm or less.
- a copper clad laminate with a carrier foil provided with a roughened layer having a fine concavo-convex structure is obtained. If this copper clad laminate with carrier foil is used, good adhesion between the insulating layer constituting material and the bulk copper layer can be obtained. Moreover, since the roughening process layer provided in the surface of carrier foil absorbs a laser beam, it becomes possible to drill a carrier foil and a bulk copper layer simultaneously using a laser.
- the copper foil with carrier foil according to the present application can be suitably used when manufacturing a multilayer printed wiring board by the build-up method and the coreless build-up method. If the copper foil with carrier foil is used, the insulating layer It can provide high-quality printed wiring boards with good adhesion to components and eliminating defects caused by splash around the hole openings formed by laser drilling. It becomes like this.
- FIG. 1 is a scanning electron microscope image of a linear circuit having a circuit width of 8 ⁇ m and an inter-circuit gap width of 8 ⁇ m obtained using the copper foil with a carrier foil for laser drilling obtained in Example 1.
- FIG. 1 is a scanning electron microscope image of a linear circuit having a circuit width of 8 ⁇ m and an inter-circuit gap width of 8 ⁇ m obtained using the copper foil with a carrier foil for laser drilling obtained in Example 1.
- the copper clad laminate according to the present application has a layer configuration as shown in FIG.
- the copper clad laminate according to the present application is obtained by laminating the copper foil 11 with carrier foil according to the present application on at least one surface of the insulating layer constituting material 5, and FIG. 1 (1-A) shows the insulating layer constituting material.
- 5 shows an example in which the copper foil 11 with carrier foil according to the present application is laminated on both surfaces of FIG. 1
- stacked is shown. In the example shown in FIG.
- the copper clad laminate 1 shown in FIG. 1 is merely an example of the copper clad laminate according to the present application, and the invention according to the present application is not limited to the layer configuration shown in FIG.
- the copper foil with carrier foil according to the present application has a layer configuration of “carrier foil 12 / peeling layer 13 / bulk copper layer 14” as shown in FIG. Roughening treatment provided on the surface of the carrier foil 12 with a “roughening treatment layer 4 having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a compound”
- the layer 4 is used as a laser light absorption layer
- the roughening treatment layer 4 provided on the surface of the bulk copper layer 14 is used as an adhesive layer with an insulating layer constituent material.
- both surfaces of the copper foil with carrier foil are the surface opposite to the side facing the release layer 13 of the carrier foil (hereinafter referred to as the outer surface of the carrier foil) and the release layer 13 of the bulk copper layer 14. This refers to the surface opposite to the side to be used (hereinafter referred to as the outer surface of the bulk copper layer).
- the outer surface of the carrier foil the surface opposite to the side to be used.
- Carrier foil The carrier foil of the copper foil with carrier foil is not particularly limited in material. However, it is considered to provide a “roughening treatment layer having a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound” on the outer surface of the carrier foil. Then, the carrier foil is preferably a foil having a copper component on the surface, such as a copper foil or a resin film coated with copper on the surface.
- the thickness of the carrier foil there is no particular limitation regarding the thickness of the carrier foil.
- a roughening treatment layer provided on the outer surface of the carrier foil is used as the laser light absorption layer. Therefore, considering the ease of laser drilling, shortening the processing time, reducing the material cost, etc., the thickness of the carrier foil is preferably in the range of 7 ⁇ m to 18 ⁇ m.
- the material and thickness of the carrier foil are not particularly limited, but the laser drilling workability when performing laser drilling by irradiating the surface of the roughened layer with laser light is not limited.
- the outer surface of the carrier foil preferably has the following surface characteristics.
- the outer surface of the carrier foil is “ratio of surface area (three-dimensional area: A ⁇ m 2 ) and two-dimensional area when a two-dimensional area of 57570 ⁇ m 2 is measured by a laser method [(A) / (57570).
- the value of “surface area ratio (B)” calculated in the above formula is preferably 1.1 or more, and more preferably 1.5 or more.
- the surface area ratio (B) is 1.1 or more, the laser drilling performance is good, and when it is 1.5 or more, it becomes even better.
- the value of the surface area ratio (B) exceeds 3.0, the thickness of the carrier foil varies, and as a result, the laser hole diameter tends to vary. For this reason, the value of the surface area ratio (B) on the outer surface of the carrier foil is preferably 3.0 or less.
- the surface roughness (Rzjis) of the outer surface of the carrier foil is preferably 2.0 ⁇ m or more.
- a roughening treatment layer having the above-mentioned fine concavo-convex structure is provided on the outer surface of a carrier foil having a surface having a surface roughness (Rzjis) of 2.0 ⁇ m or more, and the roughening treatment layer is used as a laser light absorption layer.
- the laser drilling performance can be improved.
- the rougher the surface roughness of the outer surface of the carrier foil the lower the reflectance of the laser beam on the outer surface of the carrier foil, and the better the laser drilling performance.
- the surface roughness (Rzjis) is 6.0 ⁇ m or more, the thickness of the carrier foil varies, and as a result, the laser hole diameter tends to vary. For this reason, it is preferable that the surface roughness (Rzjis) of the outer surface of the carrier foil is 6.0 ⁇ m or less.
- the release layer of the copper foil with carrier foil used in the laser drilling method according to the present application is not particularly limited as long as the carrier foil can be peeled off later, and has the characteristics required for the release layer. As long as it is satisfactory, it may be either an “organic release layer” formed using an organic component or an “inorganic release layer” formed using an inorganic component.
- an organic component that contains at least one compound selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid.
- the nitrogen-containing organic compound here includes a nitrogen-containing organic compound having a substituent.
- examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which are triazole compounds having a substituent, and 1H. It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like.
- the sulfur-containing organic compound it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, or the like.
- the carboxylic acid it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like. This is because these organic components are excellent in heat resistance at high temperatures, and it is easy to form a release layer having a thickness of 5 nm to 60 nm on the surface of the carrier foil.
- an “inorganic release layer” Ni, Mo, Co, Cr, Fe, Ti, W, P as an inorganic component, or a group consisting of an alloy or compound containing these as a main component It is possible to use at least one selected from In the case of these inorganic release layers, it can be formed using a known method such as an electrodeposition method, an electroless method, or a physical vapor deposition method.
- both the organic release layer and the inorganic release layer can be preferably used, but when the heat is applied during lamination with the insulating layer constituting material, the appropriate peeling strength of the carrier foil is provided. It is preferable to use an organic release layer from the viewpoint of ensuring stability.
- the bulk copper layer of the copper foil with carrier foil used in the present application is not particularly limited as long as it is a copper foil laminated so as to be peelable from the carrier foil via the peeling layer.
- the method for producing the copper foil constituting the bulk copper layer is not particularly limited, and the copper foil can be produced by an electrolytic plating method, an electroless plating method, a vacuum deposition method, a sputtering deposition method, a chemical vapor reaction method, or the like. It can be produced by various methods including conventionally known methods. However, considering the production cost and the like, it is preferable to manufacture the bulk copper layer by electrolytic plating.
- the thickness of the bulk copper layer is not particularly limited as long as it satisfies the thickness required when the copper layer is formed on a copper-clad laminate or a printed wiring board.
- the copper foil with carrier foil according to the present application is provided with a roughened layer as a laser absorption layer on the outer surface of the carrier foil, and is a copper-clad laminate or a printed wiring board used for laser drilling. It can be suitably used as a production material.
- the thickness of the bulk copper layer is preferably 0.1 ⁇ m to 9 ⁇ m.
- the thickness of the bulk copper layer is 9 ⁇ m or less, three layers of “carrier foil / peeling layer / bulk copper layer” can be drilled simultaneously when the outer surface of the carrier foil is irradiated with laser light.
- the thickness of the bulk copper layer exceeds 9 ⁇ m, the thickness of the entire copper foil with carrier foil becomes too thick, which is not preferable because the laser drilling performance deteriorates.
- the thickness of the bulk copper layer is less than 0.1 ⁇ m, it is difficult to obtain a bulk copper layer having a uniform layer thickness, which is not preferable.
- the thickness of the bulk copper layer is preferably thinner from the viewpoint of obtaining good laser drilling performance. Specifically, it is more preferably 5 ⁇ m or less, further preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. Moreover, the thinner the bulk copper layer is, the more preferable it is for circuit formation using the bulk copper layer. On the other hand, from the viewpoint of obtaining a bulk copper layer having a more uniform layer thickness, the thickness of the bulk copper layer is more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
- the surface characteristics of the bulk copper layer are not particularly limited. However, considering the fact that the copper foil with carrier foil is laminated on the insulating layer constituting material to form a copper-clad laminate and performing circuit formation using this copper-clad laminate, the surface characteristics of the outer surface of the bulk copper layer are Before the roughening treatment layer is provided, the following is preferable.
- the surface roughness (Rzjis) of the outer surface is preferably 2.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and further preferably 1.0 ⁇ m or less.
- the glossiness (Gs60 °) of the outer surface of the bulk copper layer is preferably 100 or more, and more preferably 300 or more.
- the fine concavo-convex structure is formed on the outer surface of the bulk copper layer having the above surface characteristics, it is possible to obtain a good adhesion with the insulating layer constituting material and a circuit having excellent high frequency characteristics. That is, in a high frequency circuit, it is required to form a circuit on a conductor having a smooth surface in order to suppress transmission loss due to the skin effect.
- the roughening layer referred to in the present application is provided on the outer surface of the bulk copper layer, there is a concern about transmission loss of the high-frequency signal due to the uneven structure provided on the outer surface.
- the fine concavo-convex structure is formed by a convex portion made of a copper composite compound containing copper oxide and cuprous oxide, a high-frequency signal is present in the roughening treatment layer made of the fine concavo-convex structure. Does not flow. For this reason, the said bulk copper layer shows the high frequency characteristic equivalent to the non-roughened copper layer which has not been roughened. Further, the roughened layer has good adhesion to the insulating material constituting the low dielectric constant used for the high frequency substrate.
- the copper foil with carrier foil provided with the roughened layer having the fine concavo-convex structure on the outer surface of the bulk copper layer serving as the adhesive surface with the insulating layer constituting material is used for the circuit formation of the high-frequency circuit forming material and the printed wiring board. It is also suitable as a material.
- both sides of the copper foil with carrier foil have “a fine concavo-convex structure formed by needle-like or plate-like convex portions having a maximum length of 500 nm or less made of a copper composite compound”.
- a roughening treatment layer is provided.
- the fine irregularities constituting the roughening layer on each surface The shape and size of the structure can be common.
- the roughening layer is described without particularly distinguishing between the roughening layer provided on the outer surface of the carrier foil and the roughening layer provided on the outer surface of the bulk copper layer, the explanation matters Is common to all roughening layers.
- the copper clad laminate with a carrier foil provided with the roughened layer having the fine concavo-convex structure on the outer surface of the carrier foil the roughened layer can be used as a laser light absorbing layer, and the carrier foil, the bulk copper layer, Can be drilled at the same time.
- the roughening process layer which has this fine concavo-convex structure is provided in the outer surface of a bulk copper layer, the favorable adhesiveness of a bulk copper layer and an insulating-layer constituent material can be obtained.
- the roughened layer is not easily damaged even if other objects touch the surface, and the convex portions forming the fine uneven structure are not damaged. So-called powder fall does not occur. Therefore, the copper foil with carrier foil according to the present application has roughening treatment layers on both surfaces, that is, the outer surface of the carrier foil and the outer surface of the bulk copper layer, but is easy to handle without powder falling off.
- FIG. 2 shows the form of the surface of the roughened layer when the roughened layer referred to in the present application is provided on the surface of a general electrolytic copper foil that can be used as a carrier foil.
- an electrolytic copper foil when used as the carrier foil, it is optional to provide the bulk copper layer on either the electrode surface side or the deposition surface side of the electrolytic copper foil. Therefore, when the electrolytic copper foil is used as a carrier foil, it is arbitrary which surface on the electrode surface side or the deposition surface side is used as the outer surface, that is, the laser light irradiation surface. Accordingly, FIG.
- each roughening treatment layer fine convex portions protruding in a needle shape or plate shape are densely adjacent to each other, so that the surface of the electrolytic copper foil is extremely fine. An uneven structure is formed, and it is observed that these convex portions are provided so as to cover the surface of the electrolytic copper foil along the surface shape of the electrolytic copper foil.
- the macroscopic surface shape of each surface is different.
- the difference in the macroscopic surface shape is considered to be caused by the difference in the macroscopic surface shape between the electrode surface and the deposition surface of the electrolytic copper foil itself before the fine uneven structure is formed.
- the electrode surface of the electrolytic copper foil becomes smooth because the surface shape of the cathode is transferred.
- the other surface side (deposition surface side) generally has an uneven shape formed by electrodeposition of copper. Referring to FIG.
- the surface of the roughening treatment layer maintains the macroscopic surface shape of each surface of the electrolytic copper foil before the roughening treatment, and the electrode surface has a relatively smooth macroscopic surface shape. It can be seen that the deposited surface has a macroscopic surface shape with irregularities. This is because the needle-like or plate-like convex portion having a maximum length of 500 nm or less covers the surface of the electrolytic copper foil along the surface shape of the electrolytic copper foil before the roughening treatment. Since it is provided densely on the surface, it is considered that the macroscopic surface shape of each surface of the electrolytic copper foil is maintained even after the fine concavo-convex structure is formed.
- the fine concavo-convex structure is formed by convex portions having a maximum length of 500 nm or less.
- the arrangement pitch at which the convex portions are arranged on the surface of the copper foil (electrolytic copper foil) is It is shorter than the length of each convex part.
- a carbon dioxide laser having a dominant wavelength of 9.4 ⁇ m and 10.6 ⁇ m is used. Since the surface of the roughened layer has an arrangement pitch of the convex portions shorter than the emission wavelength of the carbon dioxide laser, the surface of the roughened layer suppresses the reflection of the laser beam by the carbon dioxide laser, and has a high light absorption. Absorbs laser light at a rate.
- the maximum length of the convex part which forms the said fine uneven structure is 500 nm or less, and is short compared with the length of the convex part formed by the conventional blackening process.
- the convex part formed by the conventional blackening process is thin and long protruding from the surface of the copper foil, so it is easy to be damaged when other objects come into contact with the surface, so-called powder falling during handling. It was happening.
- the fine concavo-convex structure referred to in the present application does not have a convex portion that is thin and long protruding from the surface of the copper foil as in the conventional blackening treatment.
- FIG. 3 is a scanning electron microscope observation image showing a cross section of the copper foil with carrier foil referred to in the present application.
- FIG. 3 shows a cross section of the carrier foil-side copper foil on the carrier foil side.
- a portion observed in a thin line shape is a convex portion.
- the surface of the copper foil is covered with innumerable convex portions densely packed with each other, and each convex portion protrudes from the surface of the copper foil along the surface shape of the copper foil.
- the “maximum length of the convex portion” means that when the length from the base end to the tip end of each convex portion observed in the shape of the line (line segment) in the cross section of the copper foil is measured.
- the roughening treatment layer on the outer surface of the carrier foil used as the laser light absorption layer has a higher laser light absorbance as the maximum length of the convex portion is longer, and the laser drilling performance is improved.
- the roughened layer on the outer surface of the bulk copper layer used as the adhesive layer with the insulating layer constituent material has a longer maximum length of the convex portion, and the insulating layer constituent material has a smaller anchor effect. Good adhesion can be obtained.
- the maximum length of the part is preferably 400 nm or less, and more preferably 300 nm or less.
- the maximum length of the convex portion is 100 nm or more.
- the roughened layer having a fine uneven structure is visually recognized in a layered manner on the surface layer portion of the copper foil.
- the thickness of the roughening treatment layer corresponds to the length (height) in the thickness direction in which the convex portion protrudes from the surface of the copper foil.
- the length and the protruding direction of each convex portion forming the fine concavo-convex structure are not constant, and the protruding direction of each convex portion is not parallel to the thickness direction of the copper foil.
- the height of each convex portion varies. For this reason, the thickness of the roughened layer also varies.
- the average thickness of the roughened layer is 400 nm or less.
- the maximum length of the convex portion is 500 nm or less, and as described above, since there is no convex portion that protrudes long from the surface of the copper foil (carrier foil or bulk copper layer), the scratch resistance performance is high. It can be set as a roughening process layer. For this reason, handling becomes easy, good laser drilling without variation can be performed, and good adhesion between the bulk copper layer and the insulating layer constituting material can be obtained.
- the length of the tip portion that can be observed separately from the portion is 250 nm or less.
- “the length of the tip portion that can be separately observed from other convex portions refers to the length shown below.
- the convex portion protrudes in a needle shape or a plate shape on the surface of the roughened layer. Since the convex portions are densely provided on the surface of the copper layer, the base portion of the convex portion, that is, the interface between the convex portion made of the copper composite compound and the copper foil is observed from the surface of the copper layer. Can not do it. Therefore, when the roughened layer of the copper layer is observed in a plane as described above, one convex portion is separated from other convex portions among adjacent convex portions while being densely packed together.
- the portion that can be observed as being independently present is referred to as the “tip portion that can be observed separately from other convex portions”, and the length of the tip portion is the tip of the convex portion (that is, the tip) The length from the tip of the portion) to the position on the most proximal side that can be separated and observed from other convex portions.
- the maximum length of the convex portion is approximately 500 nm or less.
- the maximum length of the convex portion is long in any case, and the length of the tip portion of the convex portion is also Longer is preferred.
- the length of the tip portion of the convex portion is increased, it is likely to be damaged when another object comes into contact. Therefore, from the viewpoint of improving the scratch resistance and facilitating handling while maintaining good laser drilling performance and adhesion to the insulating layer constituent material, the length of the tip of the convex portion is longer.
- the thickness is preferably 200 nm or less, and more preferably 100 nm or less.
- the length of the tip portion of the convex portion is less than 30 nm, the laser drilling performance is lowered and the adhesion with the insulating layer constituting material is also lowered. For this reason, it is preferable that the length of the front-end
- the length of the tip portion of the convex portion is 1 ⁇ 2 or less with respect to the maximum length of the convex portion.
- the tip of the convex portion protrudes from the surface of the copper foil while being separated from other convex portions, so that the copper foil surface is densely covered with this fine uneven structure. can do.
- the specific surface area (hereinafter simply referred to as “Kr adsorption specific surface area”) measured by adsorbing krypton on the surface of the fine concavo-convex structure in the roughened layer is 0.035 m 2 / g or more. It is preferable to satisfy the conditions.
- the Kr adsorption specific surface area is 0.035 m 2 / g or more
- the average height of the convex portion in the roughened layer is on the order of 200 nm, and stable laser drilling performance and scratch resistance performance can be stably achieved. This is because it can be secured.
- the upper limit of the Kr adsorption specific surface area is not defined, the upper limit is about 0.3 m 2 / g, more preferably 0.2 m 2 / g.
- the Kr adsorption specific surface area at this time is a pretreatment by heating the sample at 300 ° C. for 2 hours using a specific surface area / pore distribution measuring device 3Flex manufactured by Micromeritics. Measured using krypton (Kr) as the adsorbed gas.
- the convex portion is made of a copper composite compound.
- the copper composite compound is most preferably copper oxide, and copper oxide is the main component.
- cuprous oxide may be contained.
- a small amount of metallic copper may be contained.
- the peak area of Cu (I) obtained by analyzing the constituent elements of the fine concavo-convex structure using X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy: hereinafter simply referred to as “XPS”)
- the ratio of the peak area of Cu (I) to the total area with the peak area of Cu (II) (hereinafter referred to as the occupied area ratio) is 50% when the roughened layer is used as a laser light absorption layer. It is preferable that it is less than.
- the exclusive area ratio of Cu (I) is preferably 50% or more.
- each peak of Cu (I) and Cu (II) can be separated and detected.
- the Cu (0) peak may be observed overlapping with the shoulder portion of the large Cu (I) peak.
- the peak of Cu (0) is observed overlappingly, it shall be considered as a Cu (I) peak including this shoulder part.
- the constituent element of the copper composite compound which forms a fine concavo-convex structure using XPS is analyzed, Cu (I) appearing at 932.4 eV corresponding to the binding energy of Cu 2p 3/2, and 934.
- Cu (I) appearing at 932.4 eV corresponding to the binding energy of Cu 2p 3/2
- 934 Each peak obtained by detecting the photoelectrons of Cu (II) appearing at 3 eV is separated into waveforms, and the occupation area ratio of the Cu (I) peak is specified from the peak areas of the respective components.
- Quantum 2000 (beam condition: 40 W, 200 ⁇ m diameter) manufactured by ULVAC-PHI Co., Ltd. is used as an XPS analyzer
- “MultiPack ver. 6.1A” is used as analysis software to perform state / semi-quantitative narrow measurement. be able to.
- the Cu (I) peak obtained as described above is considered to be derived from monovalent copper constituting cuprous oxide (cuprous oxide: Cu 2 O). And it is thought that a Cu (II) peak originates in the bivalent copper which comprises copper oxide (cupric oxide: CuO). Furthermore, it is considered that the Cu (0) peak is derived from zero-valent copper constituting metallic copper. Therefore, when the occupation area ratio of the Cu (I) peak is less than 50%, the proportion of cuprous oxide in the copper composite compound constituting the roughened layer is smaller than the proportion of copper oxide. In consideration of the laser drilling performance, the smaller the occupation ratio of the Cu (I) peak, the better.
- the occupancy rate is less than 40%, less than 30%, less than 20%, etc., the smaller the value, the better the laser drilling performance, and the occupancy rate is 0%, that is, a fine concavo-convex structure is formed. It is most preferable that the convex portion to be made of only copper oxide.
- the roughened layer on the outer surface of the bulk copper layer is the roughened layer on the outer surface of the carrier foil serving as the laser light irradiation surface.
- the copper composite compound preferably contains copper oxide and cuprous oxide, and more preferably contains cuprous oxide as a main component.
- the Cu (I) peak occupancy is preferably 50% or more, more preferably 70% or more, More preferably, it is 80% or more, and particularly preferably 90% or more.
- the occupied area ratio of the Cu (I) peak When the occupied area ratio of the Cu (I) peak is less than 50%, after performing laser drilling on the copper layer and further forming a circuit by an etching method, a fine uneven structure is formed in the etching solution. The constituent components of are easily dissolved. This is because copper oxide has higher solubility in acids such as an etchant than cuprous oxide. Therefore, when the occupied area ratio of the Cu (I) peak is less than 50%, the adhesiveness between the copper layer and the insulating layer constituting material may be lowered later, which is not preferable.
- the upper limit value of the occupied area ratio of the Cu (I) peak is not particularly limited, but is preferably 99% or less.
- the exclusive area ratio of the Cu (I) peak is preferably 98% or less, and more preferably 95% or less.
- the occupied area ratio of the Cu (I) peak is calculated by a calculation formula of Cu (I) / ⁇ Cu (I) + Cu (II) ⁇ ⁇ 100 (%).
- the fine concavo-convex structure described above is formed, for example, by applying the following wet roughening treatment to both surfaces of the copper foil with carrier foil (that is, the outer surface of the carrier foil and the outer surface of the bulk copper layer).
- the copper composite compound which has copper oxide (cupric oxide) as a main component is formed in both surfaces of copper foil with a carrier foil by oxidizing on both surfaces of copper foil with carrier foil by a wet method.
- a fine concavo-convex structure formed from needle-like or plate-like convex portions made of a copper composite compound containing copper oxide as a main component can be formed on both surfaces of the copper foil with carrier foil.
- the “fine concavo-convex structure formed from needle-like or plate-like convex portions” made of a copper composite compound to be formed can be formed on both sides or one side of a copper foil with a carrier foil.
- the “fine concavo-convex structure” itself referred to in the present application is formed at the stage of oxidation treatment.
- the roughening process may be completed without performing a reduction process after the oxidation process.
- a reduction treatment may be performed after the oxidation treatment. Even when the reduction treatment is performed, a part of the copper oxide can be reduced to cuprous oxide while maintaining the shape of the fine concavo-convex structure at the oxidation treatment stage. As a result, a “fine concavo-convex structure” made of a copper composite compound containing copper oxide and cuprous oxide can be formed.
- a small amount of metallic copper may be contained in a copper composite compound containing copper oxide as a main component or a copper composite compound containing copper oxide and cuprous oxide.
- an alkali solution such as a sodium hydroxide solution.
- an alkaline solution By oxidizing both sides of the copper foil with carrier foil using an alkaline solution, convex portions made of a copper composite compound mainly composed of needle-like or plate-like copper oxide are formed on both sides of the copper foil with carrier foil. be able to.
- both surfaces of the copper foil with carrier foil are oxidized with an alkaline solution, the convex portion grows long, and the maximum length may exceed 500 nm. It becomes difficult to form a structure. Therefore, in order to form the fine concavo-convex structure, it is preferable to use an alkaline solution containing an oxidation inhibitor capable of suppressing oxidation on both surfaces of the copper foil with a carrier foil.
- Examples of such an oxidation inhibitor include an amino silane coupling agent. If an alkaline solution containing an amino silane coupling agent is used to oxidize both sides of the copper foil with carrier foil, the amino silane coupling agent in the alkaline solution is adsorbed on both sides of the copper foil with carrier foil. The oxidation by the alkaline solution can be suppressed. As a result, the growth of needle-like crystals of copper oxide can be suppressed, and extremely fine uneven structures can be formed on both surfaces of the copper foil with carrier foil.
- amino-based silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. may be used. It can. All of these are dissolved in an alkaline solution and are stably held in the alkaline solution, and also exhibit an effect of suppressing oxidation on both sides of the copper foil with a carrier foil described above.
- the fine concavo-convex structure formed by subjecting both surfaces of the copper foil with a carrier foil to an oxidation treatment with an alkaline solution containing an amino-based silane coupling agent has a shape even after a reduction treatment. Almost maintained.
- Cu (I) obtained when qualitative analysis using XPS is performed on the constituent elements of the copper composite compound that forms the fine relief structure by adjusting the reducing agent concentration, solution pH, solution temperature, and the like.
- the area occupied by the peak of Cu (I) can be appropriately adjusted with respect to the total area of the peak area of Cu and the peak area of Cu (II). Also, for example, by immersing the copper foil with carrier foil in an alkaline solution, fine irregularities mainly composed of copper oxide on both surfaces of the copper foil with carrier foil, that is, the outer surface of the carrier foil and the outer surface of the bulk copper layer, respectively. If the structure is formed and then the reduction treatment is performed only on the roughened layer on the outer surface of the bulk copper layer, the laser light irradiation surface has a Cu (I) peak occupancy of 0%, and the insulating layer constituent material
- the bonding surface can be a copper foil with carrier foil having a Cu (I) peak occupancy of 50% or more.
- the fine concavo-convex structure is formed on both surfaces of the copper foil with a carrier foil by a method such as immersing the copper foil with a carrier foil in a treatment solution. be able to. Therefore, by using this wet method, forming a fine relief structure on both sides of the copper foil with a carrier foil improves the laser drilling processability on the laser light irradiation surface side, and the nano anchor effect by the fine relief structure Thus, the adhesion between the insulating layer constituting material and the bulk copper layer can be improved.
- the fine concavo-convex structure has high scratch resistance, so even if the fine concavo-convex structure is formed on both sides of the copper foil with carrier foil, handling is easy and prevents powder falling and the like. be able to.
- Silane coupling agent treatment In copper foil with carrier foil, moisture resistance degradation when processed into a printed wiring board by providing a silane coupling agent treatment layer on the surface of the roughening treatment layer on the outer surface of the bulk copper layer. The characteristics can be improved.
- the silane coupling agent treatment layer provided on the roughened surface is composed of olefin functional silane, epoxy functional silane, vinyl functional silane, acrylic functional silane, amino functional silane and mercapto functional silane as a silane coupling agent. Either can be used to form.
- silane coupling agents are represented by the general formula R—Si (OR ′) n (where R: an organic functional group represented by an amino group, a vinyl group, etc., OR ′: a methoxy group, an ethoxy group, etc. And n: 2 or 3).
- silane coupling agent vinyltrimethoxysilane, vinylphenyltrimethoxylane, ⁇ -methacryloxypropyltrimethoxysilane, mainly the same coupling agent used for prepreg glass cloth for printed wiring boards, ⁇ -glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N-3- (4- (3 -Aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazole silane, triazine silane, 3-acryloxypropylmethoxysilane, ⁇ -mercaptopropyltrimethoxysilane and the like can be used.
- silane coupling agents listed here do not adversely affect the characteristics after becoming a printed wiring board. Which type is used in the silane coupling agent can be appropriately selected according to the use of the copper clad laminate.
- the above-mentioned silane coupling agent contains water as a main solvent and contains the silane coupling agent component in a concentration range of 0.5 g / L to 10 g / L, and is treated at a room temperature level. It is preferable to use a liquid.
- concentration of the silane coupling agent in the silane coupling agent treatment liquid is less than 0.5 g / L, the adsorption rate of the silane coupling agent is slow, which is not suitable for general commercial profit, and the adsorption is not uniform. It becomes.
- the concentration of the silane cup agent exceeds 10 g / L, the adsorption rate is not particularly high, and the performance quality such as moisture absorption resistance is not particularly improved. .
- the adsorption method of the silane coupling agent to the surface of the roughening treatment layer using this silane coupling agent treatment liquid can employ an immersion method, a showering method, a spray method, etc., and is not particularly limited. That is, any method can be used as long as the surface of the roughened layer and the silane coupling agent treatment liquid can be brought into contact with each other and adsorbed in accordance with the process design.
- the silane coupling agent After the silane coupling agent is adsorbed on the surface of the roughening treatment layer, it is sufficiently dried to perform a condensation reaction between the —OH group on the surface of the roughening treatment layer and the adsorbed silane coupling agent. Promote and completely evaporate the water resulting from the condensation.
- the drying method at this time For example, even if an electric heater is used or a blast method that blows warm air is not particularly limited, a drying method and drying conditions corresponding to the production line may be employed.
- the silane coupling agent treatment described above is a treatment applied to the roughened layer on the outer surface of the bulk copper layer in order to improve the adhesion with the insulating layer constituent material, and the outer surface of the carrier foil. It is not necessary to apply to the roughened layer.
- the needle-shaped or plate-shaped convex portions having a maximum length of 500 nm or less constituting the fine concavo-convex structure are arranged at a pitch shorter than the wavelength of the carbon dioxide laser and shorter than the wavelength range of visible light. ing.
- the light incident on the surface of the roughened layer is attenuated as a result of repeated irregular reflection within the fine concavo-convex structure. That is, the surface of the roughening treatment layer functions as a light absorption surface, and the surface of the roughening treatment layer is darkened to black, brown, or the like as compared with that before the roughening treatment.
- the copper clad laminate according to the present application is also characterized by the color tone of the roughened layer on the outer surface of the carrier foil used as the laser light absorbing layer, and the brightness of the L * a * b * color system L * is 30 or less, more preferably 25 or less.
- the maximum length of the convex portions constituting the fine concavo-convex structure may exceed 500 nm, which is not preferable.
- the value of the lightness L * exceeds 30, even when the maximum length of the convex portion is 500 nm or less, the convex portion is not provided sufficiently densely on the outer surface of the carrier foil. There is.
- the state of the roughening treatment may be insufficient, or the state of the roughening treatment may be uneven, and the bulk copper layer is lasered via the carrier foil. This is not a state suitable for drilling and is not preferable.
- the lightness L * is 25 or less, the surface of the roughened layer becomes a more preferable state suitable for laser drilling.
- the lightness L * was measured using a spectral color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the whiteness attached to the measuring device was used for the lightness calibration in accordance with JIS Z8722: 2000.
- the value of the brightness L * is the same as that of the roughening process layer provided on the outer surface of the carrier foil. It is the same.
- the brightness L * value of the surface of the roughened layer varies before and after that. There is no.
- the copper-clad laminate 1 according to the present application is obtained by laminating the adhesive layer side of the bulk copper layer 14 of the copper foil 11 with carrier foil according to the present application on at least one surface of the insulating layer constituting material 5. Therefore, as shown to FIG. 4 (A), the surface (laser irradiation surface) by which a laser beam is irradiated becomes an outer surface of the carrier foil 12 of the copper foil 11 with carrier foil.
- the carrier foil 12 and the bulk copper layer 14 are simultaneously formed by irradiating laser light from the outer surface side of the carrier foil 12. Laser drilling can be performed. Thereafter, the carrier foil 12 is peeled off, so that the splash existing around the opening of the via hole formed by laser drilling is removed together with the carrier foil from the surface of the bulk copper layer, and the periphery of the opening is flat.
- a via hole 10 as shown in (B) can be formed.
- the surface of the roughening treatment layer becomes a black or brown matte surface and suppresses reflection of laser light.
- the thermal energy of the laser beam can be efficiently applied to the laser beam irradiation site.
- the laser light irradiation surface of the copper clad laminate is a copper layer (referred to as carrier foil or bulk copper layer; hereinafter the same)
- the surface is subjected to roughening treatment, blackening treatment, or the like. Unless otherwise, the surface of the copper layer becomes a mirror surface, and the laser light is reflected, so that the thermal energy of the laser light cannot be efficiently applied to the laser light irradiation site.
- the boiling point of copper is 2562 ° C, whereas the boiling points of copper oxide and cuprous oxide are 2000 ° C and 1800 ° C, respectively. Compared with copper, the boiling points of copper oxide and cuprous oxide are low. For this reason, when the surface of the roughening treatment layer is irradiated with laser light, the laser irradiation site on the surface of the roughening treatment layer reaches the boiling point earlier than in the case where the copper layer itself is a laser light irradiation surface.
- the thermal conductivity of copper is 354 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 at 700 ° C., whereas the thermal conductivity of copper oxide and cuprous oxide are both 20 W ⁇ m ⁇ 1 at 700 ° C.
- the thermal conductivity of copper oxide and cuprous oxide is extremely small relative to the thermal conductivity of copper.
- the melting points of copper oxide and cuprous oxide are 1201 ° C. and 1235 ° C., respectively, whereas the melting point of copper is 1083 ° C., which is low.
- part becomes slow.
- heat can be concentrated in the depth direction, and the temperature of the carrier foil and the bulk copper layer can be easily made higher than the melting point.
- by providing the fine concavo-convex structure made of the copper composite compound on the laser light irradiation surface laser drilling can be performed more efficiently than when the copper layer itself is the laser light irradiation surface.
- the printed wiring board according to the present application includes a copper layer formed using the bulk copper layer of the copper foil with carrier foil according to the present application, and is manufactured using the copper-clad laminate according to the present application. It may be.
- the copper layer is preferably provided with a via hole formed by laser drilling.
- the layer configuration and manufacturing method of the printed wiring board according to the present application are not limited to the forms described below, and the copper formed using the bulk copper layer of the copper foil with carrier foil according to the present application. Any form provided with a layer can be included.
- FIG. 5 to FIG. 7 show an example of a manufacturing process of a multilayer printed wiring board by a so-called build-up method.
- “carrier foil 12 / peeling layer 13 / bulk copper” are provided on both surfaces of an inner layer substrate 9 having an inner layer circuit 8 via an insulating layer constituting material 5 such as a prepreg / resin film.
- a copper foil 11 with a carrier foil having the layer configuration of “layer 14” is laminated to obtain a first build-up laminate 40 with a carrier foil.
- the copper foil 11 with carrier foil may be laminated only on one surface side of the insulating layer constituting material 5.
- FIG. 5 (A) “carrier foil 12 / peeling layer 13 / bulk copper” are provided on both surfaces of an inner layer substrate 9 having an inner layer circuit 8 via an insulating layer constituting material 5 such as a prepreg / resin film.
- a copper foil 11 with a carrier foil having the layer configuration of “layer 14” is laminated to obtain a first build-up laminate 40
- an inner layer substrate 9 is provided with inner layer circuits 8 on both sides thereof, and filled vias (via holes) 10 for interlayer connection are formed.
- the inner layer substrate 9 is not limited to the form shown in FIG. 5A, and any layer configuration may be used.
- laser drilling is performed by irradiating the surface of the roughened layer 4 of the carrier foil 12 of the first buildup laminate 40 with carrier foil with a laser beam.
- the carrier foil 12 is peeled off by the release layer 13 to remove all splashes present around the opening of the hole formed by the laser drilling process, and a clean bulk without splashing.
- the surface of the copper layer 14 is exposed, and the first buildup layer-equipped laminate 41 shown in FIG.
- the carrier foil 12 provided with the roughening treatment layer 4 having the fine uneven structure is present on both surfaces thereof.
- Laser drilling can be easily performed from both surfaces of the first build-up laminate 40 with carrier foil. And the desmear process for removing the resin residue produced by the laser drilling process is performed, the inside of the via hole is plated and filled to form the filled via 10, and the plated layer 24 is formed on the surface of the bulk copper layer. And the laminated body 42 with the 1st buildup wiring layer shown in FIG.7 (D) can be formed by forming the 1st buildup wiring layer 31 by carrying out an etching process. *
- FIG. 7D When the copper foil 11 with carrier foil is laminated on both surfaces of the laminate 42 with the first buildup wiring layer shown in FIG. 7D via the insulating layer constituting material 5 such as a prepreg / resin film, FIG. It becomes the 2nd buildup laminated body 43 with a carrier foil provided with the 2nd buildup wiring layer 32 shown to (E). In this way, the same operation as in FIG. 6B, FIG. 6C, and FIG. 7D is repeated as necessary to build the nth circuit pattern layer (n ⁇ 3: integer). It can also be laminated up.
- the outer surface of the bulk copper layer 14 It is also preferable to use a copper foil with a carrier foil with a resin layer provided with a resin layer for constituting an insulating layer.
- the multi-layer laminate after the final lamination is subjected to laser drilling if necessary, desmear treatment for removing the resin residue generated by laser drilling, and plating filling in the via hole A filled via is formed, and a plated layer is formed on the surface of the bulk copper layer, and then the outer copper layer is etched to form an outer layer circuit to form a multilayer printed wiring board.
- the printed wiring board according to the present application is manufactured by using the copper foil 11 with carrier foil according to the present application, and then laser drilling is performed by peeling the carrier foil 12 with the release layer 13 after the laser drilling process. All splashes present around the opening of the via hole formed in (1) can be removed. Therefore, plating filling and circuit formation in the via hole can be performed by plating processing, etching processing or the like in a state where the surface of the bulk copper layer around the opening of the via hole is clean. Further, the roughened layer 4 on the outer surface of the bulk copper layer 14 makes it possible to obtain good adhesion to the insulating layer constituting material 5 constituting the interlayer insulating layer.
- the copper foil with carrier foil according to the present application was produced as follows. First, an untreated copper foil with a carrier foil having a layer configuration of “carrier foil / peeling layer / bulk copper layer” was prepared. As the untreated copper foil with carrier foil, the surface roughness (Rzjis) of the outer surface of the carrier foil is 5.3 ⁇ m, the glossiness [Gs (60 °)] is 2.1, and the thickness of the carrier foil is The thickness was 12 ⁇ m, the bulk copper layer was 1.5 ⁇ m, and the release layer was composed of an organic release layer containing 1,2,3-benzotriazole.
- the carrier according to the present application in which the outer surface of the carrier foil of the copper foil with untreated carrier foil and the outer surface of the bulk copper layer are subjected to surface treatment in the following procedure, and the roughened layer is provided on both surfaces thereof. A copper foil with foil was obtained.
- the measuring method of surface roughness, surface area ratio, and glossiness is as follows.
- the surface area ratio (B) was determined according to the above formula based on the surface area A when a two-dimensional area of 57570 ⁇ m 2 was measured by the laser method.
- Glossiness was measured using a gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z 8741-1997, which is a glossiness measurement method.
- the copper foil with carrier foil was pretreated and then roughened. Hereinafter, it demonstrates in order.
- Pretreatment The copper foil with carrier foil was immersed in an aqueous sodium hydroxide solution, degreased with alkali, and washed with water. And this alkali-degreasing copper foil with a carrier foil was immersed in a sulfuric acid aqueous solution having a sulfuric acid concentration of 5 mass% for 1 minute, and then washed with water.
- the copper foil with carrier foil subjected to the preliminary treatment was oxidized.
- a copper compound containing copper oxide was formed on both surfaces of the copper foil with carrier foil 11 by immersing in a sodium hydroxide solution containing a predetermined oxidation treatment time (1 minute, 2 minutes, 4 minutes, 10 minutes).
- aqueous solution room temperature
- Table 1 shows the occupied area ratio of the peak of Cu (I) with respect to the total area of the peak area of Cu (I) and the peak area of Cu (II) of each sample. As a result of this qualitative analysis, the presence of “—COO group” was clearly confirmed in all samples.
- Table 1 summarizes the Kr adsorption specific surface area and brightness L * of the surface of the roughened layer on the outer surface of the carrier foil of each sample, together with the occupied area ratio of the peak of Cu (I). In Table 1, “Kr adsorption specific surface area” is simply indicated as “specific surface area”.
- the above four types of samples were respectively brought into contact with both surfaces of the insulating layer constituting material, and were laminated using a vacuum press machine under conditions of a press pressure of 3.9 MPa, a temperature of 220 ° C., and a press time of 90 minutes.
- prepreg GFPL-830NS manufactured by Mitsubishi Gas Chemical Co., Ltd. was used as the insulating layer constituent material. This obtained the copper clad laminated board which provided the copper foil with carrier foil on both surfaces of the insulating layer structural material.
- the carrier foil is peeled off, and a plated copper layer is adhered and formed on the exposed bulk copper layer, and a 18 ⁇ m thick copper layer
- the copper clad laminated board provided with this was produced.
- the test substrate provided with the linear circuit for 0.4 mm width peeling strength measurement was produced by the etching method using the said sample. And the peeling strength of each test board
- Example 2 the same untreated copper foil with carrier foil as in Example 1 was used, and oxidation treatment was performed on both surfaces of the untreated copper foil with carrier foil (pretreatment time was 2 minutes). After the treatment, the outer surface of the carrier foil was not subjected to the reduction treatment, and only the outer surface of the bulk copper layer was subjected to the reduction treatment by shower spraying the same reduction treatment solution as in Example 1. In the same manner as in Example 1, a copper foil with carrier foil provided with the fine concavo-convex structure according to the present application on the outer surface of the carrier foil and the outer surface of the bulk copper layer was obtained.
- Example 2 the occupied area ratio of the peak of Cu (I) with respect to the total area of the peak area of Cu (I) and the peak area of Cu (II) on each surface, the roughness of the carrier foil.
- the Kr adsorption specific surface area and brightness L * of the surface of the chemical treatment layer were determined. The results are shown in Table 1. The presence of “—COO group” was also clearly confirmed in the copper foil with carrier foil of Example 2. Further, a copper clad laminate was obtained in the same manner as in Example 1, a test substrate for measuring the peel strength was produced, and the peel strength was measured.
- Comparative Example 1 In Comparative Example 1, the same copper foil with carrier foil as in Example 1 was used, and the outer surface of the carrier foil was not subjected to the roughening treatment, and the conventional roughening treatment (copper sulfate type) was applied only to the outer surface of the bulk copper layer. (Roughening treatment using fine copper particles formed with a copper electrolyte). A copper clad laminate was obtained in the same manner as in Example 1 using the copper foil with carrier foil of Comparative Example 1 thus obtained.
- Comparative Example 2 In Comparative Example 2, the same untreated copper foil with carrier foil as in Example 1 was used, the same pretreatment as in Example 1 was performed, blackening treatment was performed on both sides, reduction treatment was further performed, and the outer surface of the carrier foil And the copper foil with a carrier foil provided with the conventional reduction
- the procedure of the blackening process and the reduction process will be described.
- Blackening treatment A general blackening treatment was applied to the copper foil with carrier foil after the preliminary treatment.
- Reduction treatment was performed on the copper foil with carrier foil that had been subjected to blackening treatment.
- an aqueous solution containing 35 vol.% Of “CIRCUPOSIT PB OXIDE CONVERTER 60C” 6.7 vol% and “CUPOSIT Z” 1.5 vol% which is a reduction treatment liquid manufactured by Rohm & Haas Electronic Materials Co., Ltd. It was immersed for a minute, washed with water and dried. Through these steps, a copper foil with a carrier foil provided with a general reduction blackening treatment layer was obtained.
- Example 2 Moreover, using the copper foil with a carrier foil obtained as described above, a copper clad laminate was obtained in the same manner as in Example 1, and a test substrate for measuring the peel strength was prepared, and the peel strength was obtained. Was measured.
- Table 1 shows the specific surface area, lightness L * , and outer surface of the bulk copper layer of the fine concavo-convex structure formed on the surface of the carrier foil of the copper foil with carrier foil obtained in Example 1, Example 2 and Comparative Example 2.
- stacked on the insulating layer structural material is shown.
- FIG. 8 shows a scanning electron microscope observation image of a linear circuit having a circuit width of 8 ⁇ m and an inter-circuit gap width of 8 ⁇ m manufactured using the carrier foil-attached copper foil obtained in Example 1.
- the convex portions of fine irregularities formed on the outer surface of the carrier foil of the copper foil with carrier foil according to the example The maximum length is 500 nm or less, and there is no difference in the content detected in the qualitative analysis of fine irregularities. Further, the value of the lightness L * of the surface of the roughened layer is 18 to 25 and shows a very small value. On the other hand, the value of the Kr adsorption specific surface area increases in proportion to the increase in the oxidation treatment time.
- Example and Comparative Example 1 Here, laser drilling performance is examined. Irradiating a laser beam from the carrier foil side with a carbon dioxide laser as a laser light source on the copper-clad laminate using the copper foil with carrier foil obtained in Example and the copper-clad laminate obtained in Comparative Example 1 did. At this time, the mask diameter is 2.0 mm and the pulse width is 14 ⁇ sec. The laser irradiation conditions of pulse energy 19.3mJ, offset 0.8, laser beam diameter 153 ⁇ m are adopted, and a hole with a processing diameter of 60 ⁇ m is planned to be formed in the bulk copper layer of the copper clad laminate with carrier foil. A 100-shot via hole formation test was performed on each copper-clad laminate. Then, after laser irradiation, the carrier foil was removed, and when the hole diameter formed in the bulk copper layer was 60 ⁇ m or more, it was determined that the processing was performed satisfactorily. The results are shown in Table 2.
- the aperture ratio in Table 2 is the ratio of the number of shots in which a laser shot was made by conducting a 100-shot via hole formation test.
- the opening diameter distribution is a distribution width when the opening diameter of a via hole obtained in a 100-shot via hole formation test is measured.
- Example 2 Comparison between Example and Comparative Example 2: When laser drilling performance of Comparative Example 2 was evaluated in the same manner as described above, the laser drilling performance of the copper-clad laminate of Comparative Example 2 was equivalent to that of the Example. It was. However, in the copper-clad laminate of Comparative Example 2, there was a tendency that scratches, scratches, etc. were likely to occur on the surface of the reduction blackening treatment layer on the outer surface of the carrier foil. The surface of the reduced blackening treatment layer where scratches or abrasions were generated was glossy. When the surface of the reduction blackening layer was glossy, the laser drilling performance was remarkably deteriorated, and laser drilling could not be performed on the copper-clad laminate. On the other hand, the copper foil with carrier foil for laser drilling according to the present application did not cause scratches or rubbing, and the laser drilling performance was not deteriorated.
- the copper foil with carrier foil according to the present application By using the copper foil with carrier foil according to the present application, it is possible to remove all the splash around the hole opening formed by laser drilling and provide a copper-clad laminate with a clean copper layer It becomes. As a result, it is possible to provide a high-quality multilayer printed wiring board by eliminating defects caused by the splash. Further, in the copper foil with carrier foil according to the present application, the roughened layer of the carrier foil and the bulk copper layer is “formed by a needle-like or plate-like convex portion having a maximum length of 500 nm or less made of a copper composite compound. By using the “fine concavo-convex structure”, it becomes possible to form a fine pitch circuit more than conventional.
- the copper foil with carrier foil according to the present application it is possible to manufacture a multilayer printed wiring board by a build-up method and a coreless build-up method without requiring a process change of the conventional manufacturing method, and a high quality A printed wiring board can be provided.
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Abstract
Description
本件出願に係るキャリア箔付銅箔は、キャリア箔/剥離層/バルク銅層の層構成を備えるキャリア箔付銅箔であって、当該キャリア箔付銅箔の両面に、銅複合化合物からなる最大長さが500nm以下の針状又は板状の凸状部により形成された微細凹凸構造を有する粗化処理層を備え、当該キャリア箔の表面に備えられた粗化処理層はレーザー光吸収層として用いられ、当該バルク銅層の表面に備えられた粗化処理層は絶縁層構成材との接着層として用いられることを特徴とする。
本件出願に係る銅張積層板は、本件出願に係るキャリア箔付銅箔の前記バルク銅層の前記接着層側を絶縁層構成材の少なくとも片面に積層したことを特徴とする。
本件出願に係るプリント配線板は、本件出願に係るキャリア箔付銅箔の前記バルク銅層を用いて形成されたことを特徴とする。
1.銅張積層板の層構成の概念
本件出願に係る銅張積層板は、例えば、図1に示すような層構成を備える。本件出願に係る銅張積層板は、本件出願に係るキャリア箔付銅箔11を絶縁層構成材5の少なくとも片面に積層したものであり、図1(1-A)には、絶縁層構成材5の両面にそれぞれ本件出願に係るキャリア箔付銅箔11を積層した例を示し、図1(1-B)には、絶縁層構成材5の片面に本件出願に係るキャリア箔銅箔11を積層した例を示している。なお、図1(1-B)に示す例では、絶縁層構成材5の他面側には他の銅箔2が積層されている。但し、図1に示す銅張積層板1は、本件出願に係る銅張積層板の単なる一例であり、本件出願に係る発明は図1に示す層構成に限定解釈されるものではない。
まず、本件出願に係るキャリア箔付銅箔に関して述べる。本件出願に係るキャリア箔付銅箔は、図1に示すように「キャリア箔12/剥離層13/バルク銅層14」の層構成を備え、当該キャリア箔付銅箔の両面に、「銅複合化合物からなる最大長さが500nm以下の針状又は板状の凸状部により形成された微細凹凸構造を有する粗化処理層」4を備え、当該キャリア箔12の表面に備えられた粗化処理層4はレーザー光吸収層として用いられ、当該バルク銅層14の表面に備えられた粗化処理層4は絶縁層構成材との接着層として用いられることを特徴とする。なお、キャリア箔付銅箔の両面とは、キャリア箔の剥離層13に面する側とは反対側の表面(以下、キャリア箔の外表面)、及び、バルク銅層14の剥離層13に面する側とは反対側の表面(以下、バルク銅層の外表面)をいう。当該キャリア箔付銅箔を用いて銅張積層板を製造すれば、バルク銅層側の粗化処理層により、絶縁層構成材との良好な密着性を得ることができ、キャリア箔側の粗化処理層によりレーザー穴明け加工性能の良好な銅張積層板を得ることができる。以下、各構成要素毎に述べる。
本件出願において、キャリア箔付銅箔の両面には、「銅複合化合物からなる最大長さが500nm以下の針状又は板状の凸状部により形成された微細凹凸構造」を有する粗化処理層が設けられる。ここで、キャリア箔付銅箔のキャリア箔の外表面に設けられる粗化処理層と、バルク銅層の外表面に設けられる粗化処理層において、各面の粗化処理層を構成する微細凹凸構造の形状や大きさ等は共通のものとすることができる。以下において、粗化処理層について、キャリア箔の外表面に設けられる粗化処理層と、バルク銅層の外表面に設けられる粗化処理層とを特に区別せずに説明した場合、その説明事項はいずれの粗化処理層にも共通するものとする。
キャリア箔付銅箔において、上記バルク銅層の外表面の粗化処理層の表面に、シランカップリング剤処理層を設けることで、プリント配線板に加工したときの耐吸湿劣化特性を改善することができる。当該粗化処理面に設けるシランカップリング剤処理層は、シランカップリング剤としてオレフィン官能性シラン、エポキシ官能性シラン、ビニル官能性シラン、アクリル官能性シラン、アミノ官能性シラン及びメルカプト官能性シランのいずれかを使用して形成することが可能である。これらのシランカップリング剤は、一般式 R-Si(OR’)nで示される(ここで、R:アミノ基やビニル基などに代表される有機官能基、OR’:メトキシ基またはエトキシ基などに代表される加水分解基、n:2または3である。)。
上述したとおり微細凹凸構造を構成する最大長さが500nm以下の針状又は板状の凸状部は、炭酸ガスレーザーの波長よりも短く、且つ、可視光の波長域よりも短いピッチで配列されている。当該粗化処理層の表面に入射した光は、微細凹凸構造内で乱反射を繰り返す結果、減衰する。つまり、当該粗化処理層の表面は吸光面として機能し、当該粗化処理層の表面は粗化処理前と比較すると黒色、茶褐色等に暗色化する。即ち、本件出願に係る銅張積層板は、レーザー光吸収層として用いられるキャリア箔の外表面の粗化処理層の表面の色調にも特色があり、L*a*b*表色系の明度L* が30以下、より好ましくは25以下である。この明度L* の値が30を超えて明るい色調となると、当該微細凹凸構造を構成する上記凸状部の最大長さが500nmを超える場合があるため好ましくない。また、明度L* の値が30を超える場合、上記凸状部の最大長さが500nm以下であっても、当該凸状部がキャリア箔の外表面に十分に密集して設けられていない場合がある。つまり、明度L* の値が30を超える場合、粗化処理の状態が不十分である、又は、粗化処理の状態にムラがあることが考えられ、キャリア箔を介してバルク銅層にレーザー穴明け加工に適した状態ではなく、好ましくない。そして、この明度L* が25以下になると、上記粗化処理層の表面はレーザー穴明け加工に適したより好ましい状態となる。なお、明度L* の測定は、日本電色工業株式会社製 分光色差計 SE2000を用いて、明度の校正には測定装置に付属の白色板を用い、JIS Z8722:2000に準拠して行った。そして、同一部位に関して3回の測定を行い、3回の明度L* の測定データの平均値を、本件出願にいう明度L* の値としている。なお、バルク銅層の外表面に設ける粗化処理層についても、絶縁層構成材との良好な密着性を得る上でも、明度L*の値はキャリア箔の外表面に設ける粗化処理層と同様である。但し、バルク銅層の外表面に設けた粗化処理層に対して上述のシランカップリング剤処理を施した場合でも、その前後において、当該粗化処理層の表面の明度L*の値に変動はない。
次に、図4を参照しながら、上記銅張積層板を用いてレーザー穴明け加工を施す方法について説明する。ここでは、図1(1-A)に示す態様と同様の層構成を有する銅張積層板1にレーザー穴明け加工を施す場合を例に挙げて説明する。本件出願に係る銅張積層板1は絶縁層構成材5の少なくとも片面に、本件出願に係るキャリア箔付銅箔11のバルク銅層14の接着層側を積層したものである。従って、図4(A)に示すように、レーザー光が照射される側の面(レーザー照射面)は、キャリア箔付銅箔11のキャリア箔12の外表面となる。キャリア箔12の外表面には上記微細凹凸構造を有する粗化処理層が備えられているため、キャリア箔12の外表面側からレーザー光を照射すればキャリア箔12とバルク銅層14とを同時にレーザー穴明けを行うことができる。その後、キャリア箔12を引き剥がすことで、レーザー穴明け加工で形成したビアホールの開口部の周囲に存在するスプラッシュがキャリア箔と共にバルク銅層の表面から除去され、開口部の周囲が平坦な図4(B)に示すようなビアホール10を形成することができる。
本件出願に係るプリント配線板は、本件出願に係るキャリア箔付銅箔のバルク銅層を用いて形成された銅層を備えることを特徴とし、本件出願に係る銅張積層板を用いて製造されたものであってもよい。また、本件出願に係るプリント配線板において、当該銅層にはレーザー穴明け加工により形成されたビアホールを備えることも好ましい。例えば、図5~図7に示すようなビルドアップ工程により製造された多層プリント配線板とすることができる。
小坂研究所製の触針式表面粗さ計 SE3500を用い、JIS B 0601-2001に準拠して表面粗度の測定を行った。
株式会社キーエンス レーザーマイクロスコープ VK-X100を用い、57570μm2の二次元領域をレーザー法により測定したときの表面積Aに基づいて、上述した計算式に従って表面積比(B)を求めた。
日本電色工業株式会社製光沢計PG-1M型を用い、光沢度の測定方法であるJIS Z 8741-1997に準拠して、光沢度の測定を行った。
比較例1では、実施例1と同じキャリア箔付銅箔を用い、そのキャリア箔の外表面には粗化処理を施さず、バルク銅層の外表面にのみ従来の粗化処理(硫酸銅系銅電解液で形成する微細銅粒子を用いた粗化処理)を施した。このようにして得られた比較例1のキャリア箔付銅箔を用いて、実施例1と同様にして銅張積層板を得た。
比較例2では、実施例1と同じ未処理のキャリア箔付銅箔を用い、実施例1と同じ予備処理を施し、両面に黒化処理を施し、更に還元処理を施し、キャリア箔の外表面及びバルク銅層の外表面に、従来の還元黒化処理層を備えたキャリア箔付銅箔を得た。以下、黒化処理及び還元処理の手順を説明する。
以下の表1に、実施例1、実施例2及び比較例2で得られたキャリア箔付銅箔のキャリア箔表面に形成した微細凹凸構造の比表面積、明度L* 、バルク銅層の外表面の粗化処理層側を絶縁層構成材に積層したときの引き剥がし強さに関する測定結果を示す。また、図8に実施例1で得られたキャリア箔付銅箔を用いて作製した回路幅8μm/回路間ギャップ幅8μmの直線回路の走査型電子顕微鏡観察像を示す。
2 銅箔
3 電極面側の粗化処理面
4 析出面側の粗化処理面
5 絶縁層構成材
8 内層回路
9 内層基板
10 フィルドビア(ビアホール)
11 キャリア箔付銅箔
12 キャリア箔
13 剥離層
14 バルク銅層
23 第1ビルドアップ配線回路
24 めっき層
31 第1ビルドアップ配線層
32 第2ビルドアップ配線層
40 キャリア箔付第1ビルドアップ積層体
41 第1ビルドアップ層付積層体
42 第1ビルドアップ配線層付積層体
43 キャリア箔付第2ビルドアップ積層体
Claims (13)
- キャリア箔/剥離層/バルク銅層の層構成を備えるキャリア箔付銅箔であって、
当該キャリア箔付銅箔の両面に、銅複合化合物からなる最大長さが500nm以下の針状又は板状の凸状部により形成された微細凹凸構造を有する粗化処理層を備え、
当該キャリア箔の表面に備えられた粗化処理層はレーザー光吸収層として用いられ、
当該バルク銅層の表面に備えられた粗化処理層は絶縁層構成材との接着層として用いられることを特徴とするキャリア箔付銅箔。 - X線光電子分光分析法により前記微細凹凸構造の構成元素を分析したときに得られるCu(I)のピーク面積と、Cu(II)のピーク面積との合計面積に対して、Cu(I)のピーク面積が占める割合が、前記レーザー光吸収層としての粗化処理層が50%未満であり、前記接着層としての粗化処理層が50%以上である請求項1に記載のキャリア箔付銅箔。
- 前記レーザー光吸収層としての粗化処理層は、酸化銅を主成分とする銅複合化合物からなる前記微細凹凸構造を有し、前記接着層としての粗化処理層は、亜酸化銅を主成分とする銅複合酸化物からなる前記微細凹凸構造を有する請求項1又は請求項2に記載のキャリア箔付銅箔。
- 走査型電子顕微鏡を用いて、傾斜角45°、50000倍以上の倍率で前記粗化処理層を観察したときに、互いに隣接する凸状部のうち、他の凸状部と分離観察可能な先端部分の長さが250nm以下である請求項1~請求項3のいずれか一項に記載のキャリア箔付銅箔。
- 前記凸状部の前記最大長さに対して、前記凸状部の前記先端部分の長さが1/2以下である請求項4に記載のキャリア箔付銅箔。
- 前記粗化処理層の表面にクリプトンを吸着して測定した比表面積が0.035m2/g以上である請求項1~請求項5のいずれか一項に記載のキャリア箔付銅箔。
- 前記粗化処理層の表面をL*a*b*表色系で表したときの明度L*が30以下である請求項1~請求項6のいずれか一項に記載のキャリア箔付銅箔。
- 前記粗化処理層を57570μm2の二次元領域をレーザー法で測定したときの表面積を三次元表面積(Aμm2)とし、前記二次元領域の面積に対する三次元表面積の比をBとしたとき、Bが1.1以上である請求項1~請求項7のいずれか一項に記載のキャリア箔付銅箔。
- 前記バルク銅層の前記接着層側の表面粗さ(Rzjis)が2.0μm以下である請求項1~請求項8のいずれか一項に記載のキャリア箔付銅箔。
- 前記バルク銅層の前記接着層側の面にはシランカップリング剤処理が施される請求項1~請求項9のいずれか一項に記載のキャリア箔付銅箔。
- 請求項1~請求項10のいずれか一項に記載のキャリア箔付銅箔の前記バルク銅層の前記接着層側を絶縁層構成材の少なくとも片面に積層したことを特徴とする銅張積層板。
- 請求項1~請求項10のいずれか一項に記載のキャリア箔付銅箔の前記バルク銅層を用いて形成された銅層を備えることを特徴とするプリント配線板。
- 前記銅層には、レーザー穴明け加工により形成されたビアホールを備える請求項12に記載のプリント配線板。
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JP6962803B2 (ja) * | 2017-12-11 | 2021-11-05 | Dowaホールディングス株式会社 | クラッド材およびその製造方法 |
EP3857246A1 (de) * | 2018-11-02 | 2021-08-04 | Klaus Faber AG | VERFAHREN ZUR ELEKTRISCHEN MESSUNG UND VERWENDUNG EINER MESSTECHNIK ZUR BESTIMMUNG DES VERSCHLEIßZUSTANDES VON ELEKTRISCHEN LEITUNGEN, SOWIE KABELVERSCHLEIßZUSTANDSMESSVORRICHTUNG |
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WO2021079952A1 (ja) * | 2019-10-25 | 2021-04-29 | ナミックス株式会社 | 複合銅部材 |
KR102454686B1 (ko) * | 2020-12-30 | 2022-10-13 | 에스케이씨 주식회사 | 표면 처리 동박 및 이를 포함하는 회로 기판 |
WO2024043581A1 (ko) * | 2022-08-24 | 2024-02-29 | 코오롱인더스트리 주식회사 | 절연 필름 및 이를 포함하는 적층체 |
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