WO2014136763A1 - Copper foil for laser processing, carrier-foil-supported copper foil for laser processing, copper-clad laminate, and process for producing printed wiring board - Google Patents
Copper foil for laser processing, carrier-foil-supported copper foil for laser processing, copper-clad laminate, and process for producing printed wiring board Download PDFInfo
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- WO2014136763A1 WO2014136763A1 PCT/JP2014/055446 JP2014055446W WO2014136763A1 WO 2014136763 A1 WO2014136763 A1 WO 2014136763A1 JP 2014055446 W JP2014055446 W JP 2014055446W WO 2014136763 A1 WO2014136763 A1 WO 2014136763A1
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- copper foil
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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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- 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
-
- 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
- H05K3/0038—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material combined with laser drilling through a metal layer
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0358—Resin coated copper [RCC]
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/095—Conductive through-holes or vias
- H05K2201/09509—Blind vias, i.e. vias having one side closed
Definitions
- the present invention relates to a copper foil for laser processing, and in particular, relates to a copper foil for laser processing suitable for a printed wiring board manufacturing material, a copper foil for laser processing with a carrier foil, a copper clad laminate, and a method for manufacturing a printed wiring board.
- a multilayer printed wiring board is obtained by laminating three or more wiring layers via an insulating layer, and electrically connecting each wiring layer by an interlayer connection means such as a via hole or a through hole.
- a build-up method is known as a method for manufacturing a printed wiring board.
- the build-up method is a manufacturing method in which a wiring layer is laminated on an inner layer circuit via an insulating layer, and multilayered while performing interlayer connection. For example, when an ultrahigh-definition wiring pattern is formed by the modified-semi-additive method (MSAP method) or the like, a build-up printed wiring board is manufactured by the following procedure.
- MSAP method modified-semi-additive method
- a copper foil is laminated via an insulating layer on a core substrate or the like provided with an inner layer circuit, via holes are formed by laser processing or the like, and interlayer connection is performed by an electroless plating method.
- the seed layer under the plating resist is removed by etching together with the plating resist.
- micro via holes having a top diameter of 100 ⁇ m or less.
- Such micro via holes are generally drilled by laser processing using a carbon dioxide laser or the like.
- a Cu direct method is often employed in which a carbon dioxide laser or the like is directly irradiated from above the copper foil to simultaneously perforate the copper foil and the insulating layer.
- copper has a very low absorptivity of laser light in the far-infrared to infrared wavelength region such as a carbon dioxide laser, so when forming micro via holes by the Cu direct method, copper such as blackening treatment is used in advance. It was necessary to perform a pretreatment to increase the absorption rate of the laser beam on the foil surface.
- Patent Document 1 describes a copper foil in which an alloy layer mainly composed of Sn and Cu is provided on the surface of the copper foil as a technique that eliminates the need for pretreatment during laser processing.
- Sn has a laser absorption rate that is twice or more higher than that of Cu, so an alloy layer mainly composed of Sn and Cu is provided on the copper foil surface.
- a via hole having a diameter of 100 ⁇ m can be formed by directly irradiating the surface of the copper foil with laser light without performing a pretreatment such as a blackening treatment.
- the copper foil for laser drilling described in Patent Document 1 is provided with a metal Sn layer by vapor deposition or plating on the surface of the copper foil, and then Sn and Cu on the surface of the copper foil by heat diffusion treatment. Is used as an alloy layer. For this reason, in the said alloy layer, distribution will arise in Sn content in the thickness direction, and it will be thought that the etching rate in the thickness direction of the said copper foil varies. Further, the outermost surface of the copper foil has a very high Sn content, and the copper foil described in Patent Document 1 is considered to have a three-layer structure of an Sn layer, an alloy layer of Sn and Cu, and a copper layer in order from the surface layer. It is done.
- the metal Sn layer is not soluble in an etching solution for a general copper foil, when the copper foil described in Patent Document 1 is used, it is difficult to dissolve and remove the outermost surface by etching. Therefore, when the copper foil described in Patent Document 1 is used, in the etching process, after removing the outermost surface of the copper foil with a metal Sn layer etching solution capable of dissolving Sn in advance, The lower layer needs to be etched, and the etching process becomes complicated. Further, since the alloy layer of Sn and Cu described in Patent Document 1 is an alloyed layer by thermal diffusion, it is considered that the metal composition in the thickness direction is not uniform, and the etching rate in the thickness direction varies. Can occur.
- the copper foil cannot be etched with a uniform thickness, and the thickness of the copper foil may vary. Furthermore, it is considered that the etching rate of the surface of the alloy layer is slower than that of the wiring pattern portion formed by electrolytic copper plating when the Sn content is high. For this reason, when the seed layer is removed, the wiring pattern portion is etched faster, the line width becomes narrower, and it is difficult to obtain a good wiring pattern.
- the present invention provides a copper foil for laser processing, a copper foil for laser processing with a carrier foil, a copper-clad laminate, and a method for producing a printed wiring board that is excellent in laser processability and capable of forming a wiring pattern satisfactorily.
- the purpose is to provide.
- the present inventors have achieved the above object by employing the following copper foil for laser processing.
- the copper foil for laser processing according to the present invention has an etching property with respect to a copper etching solution, has an etching rate slower than that of the copper foil, and a hardly soluble laser absorbing layer that absorbs infrared laser light on the surface of the copper foil. It is characterized by having.
- the hardly soluble laser absorbing layer is preferably an electrolytic copper-tin alloy layer formed by an electrolytic plating method with a tin content of 25 mass% or more and 50 mass% or less.
- the thickness of the hardly soluble laser absorbing layer is preferably 3 ⁇ m or less.
- the thickness of the copper foil is preferably 7 ⁇ m or less.
- the other surface of the copper foil is provided with at least one of a roughening treatment layer and a primer resin layer.
- the copper foil for laser processing with a carrier foil according to the present invention is characterized in that the carrier foil is detachably provided on the hardly soluble laser absorbing layer.
- the copper foil for laser processing and the insulating layer constituting material are laminated so that the hardly soluble laser absorption layer is disposed on the side irradiated with the infrared laser light. It is characterized by that.
- the method for manufacturing a printed wiring board according to the present invention has an etching property with respect to a copper etching solution, has an etching rate slower than that of the copper foil, and includes a laser absorption layer that absorbs infrared laser light on the surface of the copper foil.
- a via hole for interlayer connection is formed by directly irradiating a poorly soluble laser absorption layer with infrared laser light on a laminate in which a copper foil for laser processing and another conductor layer are laminated via an insulating layer.
- the micro-etching process as a pretreatment of the desmear process and / or the electroless plating process for removing smear in the via hole, the hardly soluble laser absorbing layer is removed from the surface of the copper foil.
- the copper foil for laser processing according to the present invention is excellent in laser processability, and a uniform etching rate in the thickness direction can be obtained in the subsequent etching process.
- the total manufacturing cost can be reduced.
- the hardly soluble laser absorbing layer can function as an etching resist, the surface of the copper foil (layer) is dissolved in various etching steps before the formation of the wiring pattern, resulting in variations in the thickness of the copper foil (layer). Can be prevented. For this reason, a wiring pattern can be formed with a favorable etching factor.
- FIG. 1 It is a figure which shows the relationship between the tin content of the electrolytic metal foil which concerns on this invention, and an etching rate. It is a figure for demonstrating an example of the manufacturing method of the printed wiring board which concerns on this invention. It is a figure for evaluating the etching property of the electrolytic copper foil in the copper clad laminated board produced by the Example and the comparative example 1.
- FIG. 1 shows the relationship between the tin content of the electrolytic metal foil which concerns on this invention, and an etching rate. It is a figure for demonstrating an example of the manufacturing method of the printed wiring board which concerns on this invention. It is a figure for evaluating the etching property of the electrolytic copper foil in the copper clad laminated board produced by the Example and the comparative example 1.
- Copper foil for laser processing The copper foil for laser processing according to the present invention has an etching property with respect to a copper etching solution, an etching rate that is slower than that of the copper foil, and a hardly soluble laser absorbing layer that absorbs infrared laser light. It is provided on the surface of the copper foil.
- the copper foil for laser processing according to the present invention provides laser light to the surface of the copper foil for laser processing without performing pretreatment such as blackening treatment by the Cu direct method in the manufacturing process of the printed wiring board. By direct irradiation, micro holes such as micro via holes can be formed by laser processing.
- the hardly soluble laser absorbing layer is, for example, a copper layer containing an infrared laser absorbing metal material having absorbability with respect to infrared laser light, and by containing the infrared absorbing material in the copper layer, It is preferable to use a copper layer containing an infrared laser-absorbing metal material capable of making the etching rate for the copper etching solution slower than the etching rate of the copper foil.
- Specific examples of the hardly soluble laser absorbing layer include an electrolytic copper-tin alloy layer containing 25% by mass or more and 50% by mass or less of tin formed by an electrolytic plating method. In the present embodiment, the following description will be made mainly assuming that this electrolytic copper-tin alloy layer is used as the hardly soluble laser absorbing layer.
- Electrolytic copper-tin alloy layer First, the electrolytic copper-tin alloy layer will be described. Tin has a higher absorption rate of laser light (carbon dioxide laser light, etc.) having a wavelength in the far-infrared to infrared wavelength range compared to copper. That is, the electrolytic copper-tin alloy layer can function as a laser light absorption layer, and as described above, the pretreatment at the time of drilling by the Cu direct method can be eliminated.
- the electrolytic copper-tin alloy layer is etched on the surface of the copper foil in various etching processes performed in a desmear process, a micro-etching process, etc. performed after drilling and before forming a wiring pattern.
- the electrolytic copper-tin alloy layer is etched in various etching processes performed before these wiring patterns are formed.
- the timing at which the electrolytic copper-tin alloy layer is dissolved and removed can be controlled by its tin content and thickness. Therefore, it is possible to dissolve and remove only the electrolytic copper-tin alloy layer without dissolving the surface of the copper foil before the electroless plating step for interlayer connection. Therefore, for example, when a wiring pattern is formed by the MSAP method, an electroless plating film can be formed on a copper foil in which the original thickness is maintained, and a seed layer having a uniform thickness can be obtained. .
- Tin content in the present invention when an electrolytic copper-tin alloy layer is used as the hardly soluble laser absorption layer, the tin content in the electrolytic copper-tin alloy layer is 25% by mass or more as described above. This is because the function as an etching resist is exhibited. As shown in FIG. 1, when the tin content in the electrolytic copper-tin alloy layer is less than 25% by mass, the etching rate of the electrolytic copper-tin alloy layer is compared with that of the electrolytic copper foil having a tin content of 0% by mass. Then it will be faster.
- the etching rate is slow as compared with a normal electrolytic copper foil containing no tin. Therefore, by setting the tin content in the electrolytic copper-tin alloy layer to 25% by mass or more, as described above, the electrolytic copper-tin alloy layer can function as an etching resist, and before the wiring pattern is formed, It is possible to prevent the copper foil from being melted and causing variations in the thickness of the copper foil during various etching processes to be performed.
- This specification describes an invention relating to specific tin mass% when the total content of copper and tin in the copper-tin alloy layer is 100 mass%.
- the electrolytic copper-tin alloy layer is composed of the obtained copper-tin alloy deposited on the surface of the copper foil by the electrolytic plating method, the metal composition in the thickness direction becomes uniform, and the electrolytic copper-tin alloy The etching rate of the layer can be made uniform in the thickness direction. Therefore, the electrolytic copper-tin alloy layer can be dissolved at a uniform rate in the thickness direction in various etching processes performed before the wiring pattern is formed. As shown in FIG. 1, the etching rate decreases as the tin content increases. Therefore, as described above, the electrolytic copper-tin alloy layer can be dissolved and removed at an appropriate timing by adjusting the tin content and thickness in the electrolytic copper-tin alloy layer.
- an electroless plating film is formed on the surface of the copper foil with the original thickness maintained. Can do. Therefore, for example, when a wiring pattern is formed by the MSAP method, a seed layer having a uniform thickness can be formed. Therefore, when the seed layer is removed in a flash etching process after the wiring pattern is formed, Since it has a uniform composition in the thickness direction, the seed layer can be dissolved and removed at a uniform etching rate. As described above, it is possible to form a wiring pattern having a good etching factor.
- the wiring pattern is formed not only by the MSAP method but also by a method including an etching process such as a subtractive method.
- the electrolytic copper-tin alloy layer can be removed to expose the copper foil (layer) with the initial thickness maintained. A layer can be obtained, and a wiring pattern having a good etching factor can be formed.
- the etching rate of the electrolytic copper foil not containing tin is 100
- the etching rate of the electrolytic copper-tin alloy foil having a tin content exceeding 50% by mass is less than 3. Accordingly, if the tin content in the electrolytic copper-tin alloy layer exceeds 50% by mass, the etching rate with respect to the copper etching solution becomes too slow. Therefore, during various etching processes performed before the wiring pattern is formed. It becomes difficult to dissolve and remove the electrolytic copper-tin alloy layer. In particular, as shown in FIG.
- the tin content in the electrolytic copper-tin alloy layer is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.
- the etching rates of the electrolytic copper-tin alloy foil are 4 (tin content: 45 mass%) and 13 (tin content: 40 mass), respectively. %), 25 (tin content: 35 mass%).
- the etching rate of the electrolytic copper-tin alloy foil with respect to the copper etching solution is faster than the etching rate of the copper foil not containing tin.
- the etching rate shown in FIG. 1 is that electrolytic copper-tin alloy foils (thickness: 3 ⁇ m) having different tin contents (mass%) were prepared, and each electrolytic copper-tin alloy foil was subjected to a sulfuric acid-hydrogen peroxide etching solution.
- etching amount ( ⁇ m) per unit time obtained by immersing in 30 seconds, washing with water and drying, then measuring the thickness by cross-sectional observation, and obtaining the thickness reduced by etching.
- the tin content here can be measured by the following method.
- a solution in which the copper foil for laser processing as a sample is completely dissolved is subjected to ICP analysis, fluorescent X-ray apparatus, titration determination
- the amount of copper contained in the electrolytic copper-tin alloy layer was calculated by measuring the total copper content using a method, etc., and subtracting the “copper amount converted from the cross-sectional thickness of the copper foil” from this total copper content.
- tin content (% by mass) can be calculated.
- the thickness of the copper foil is known in advance by cross-sectional observation, etc., using a fluorescent X-ray film thickness measuring instrument, perform a composition analysis of the foil defined as a two-layer foil, and in the electrolytic copper-tin alloy layer The tin content (% by mass) can be calculated.
- the thickness of the electrolytic copper-tin alloy layer can be set to an appropriate value depending on the thickness and use of the laser processing copper foil. However, in consideration of dissolving and removing the electrolytic copper-tin alloy layer by etching at an appropriate stage before forming the wiring pattern, it is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less. On the other hand, if the thickness of the electrolytic copper-tin alloy layer is less than 0.1 ⁇ m, it is difficult to achieve the purpose of improving the absorption rate of the laser beam, and in various etching processes performed before forming the wiring pattern. In some cases, the electrolytic copper-tin alloy layer cannot function sufficiently as an etching resist for copper foil.
- the thickness of the electrolytic copper-tin alloy layer is preferably 0.3 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
- the etching rate for the copper etching solution varies depending on the tin content in the electrolytic copper-tin alloy layer. Therefore, the thickness of the electrolytic copper-tin alloy layer is appropriately determined according to the tin content. An appropriate value is preferable.
- any copper etchant can be used without particular limitation as long as it is an etchant generally used as an etchant for copper.
- various copper etching solutions such as copper chloride etching solution, iron chloride etching solution, sulfuric acid-hydrogen peroxide etching solution, sodium persulfate etching solution, ammonium persulfate etching solution, potassium persulfate etching solution, etc. Can be used.
- the copper foil refers to a metal foil having a copper content of 99% by mass or more, and refers to a tin-free copper foil that does not contain tin except for inevitable impurities.
- the copper foil may be either an electrolytic copper foil or a rolled copper foil. However, in view of economy and production efficiency, an electrolytic copper foil is more preferable.
- the copper foil is a layer that is bonded to an insulating layer constituting material and constitutes a part of a seed layer or the like when a multilayer printed wiring board is manufactured.
- the thickness of the copper foil can be the same as that of a commercially available copper foil as a general printed wiring board material.
- the copper foil is preferably thin from the viewpoint of obtaining a better etching factor, and is 7 ⁇ m or less. Is preferred.
- the thickness of the copper foil is 3 ⁇ m or less from the viewpoint of forming a finer wiring pattern with a good etching factor. It is more preferably a thin electrolytic copper foil, and further preferably 2 ⁇ m or less. However, when the copper foil has a thickness of 7 ⁇ m or less, it is preferably used in the form of a copper foil for laser processing with a carrier foil, which will be described later, so as not to cause problems such as wrinkles and tearing during handling.
- the surface of the copper foil that is bonded to the interlayer insulating layer that is, the surface opposite to the surface on which the electrolytic copper-tin alloy layer is provided (hereinafter referred to as the bonding surface) It is preferably smooth.
- the surface roughness (Rzjis) of the adhesion surface is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
- the surface roughness of the said adhesion surface points out the surface roughness of the adhesion surface after forming a roughening process layer.
- a roughening treatment layer is provided on the adhesive surface of the copper foil, that is, the surface opposite to the surface on which the electrolytic copper-tin alloy layer is provided. Also good.
- the roughening treatment layer can be formed by a method of depositing and forming fine metal particles on the surface (bonding surface) of the copper foil, a method of forming a roughened surface by an etching method, or the like.
- the method for forming the roughened layer may be any method as long as the adhesion between the copper foil and the insulating layer can be physically improved. Can be adopted.
- Primer resin layer In the copper foil for laser processing according to the present invention, a primer resin layer may be provided on the adhesive surface of the copper foil.
- the primer resin layer is an adhesive layer having good adhesion to both the copper foil and the insulating layer constituting material.
- the primer resin layer can be a layer made of a resin composition containing an epoxy resin or an aromatic polyamide resin.
- the thickness of the primer resin layer is not particularly limited as long as the adhesion between the copper foil and the insulating layer constituting material can be improved.
- the thickness of the primer resin layer can be in the range of 0.5 ⁇ m to 10 ⁇ m.
- the roughening process layer and the primer resin layer may be simultaneously provided in the adhesive surface of copper foil.
- the hardly soluble laser absorbing layer is the above-mentioned electrolytic copper-tin alloy layer
- an electrolytic solution containing copper ions and tin ions is used.
- the copper foil for laser processing can be obtained by laminating an electrolytic copper-tin alloy layer having a tin content of 25 mass% or more and 50 mass% or less on the copper foil by an electrolytic plating method, its production method is particularly limited. It is not something.
- various surface treatment layers such as a rust prevention treatment layer and a silane coupling treatment layer may be provided on the adhesive surface of the copper foil as required. It is.
- the copper foil for laser processing with carrier foil is provided with the carrier foil peelable on the hardly soluble laser absorbing layer of the copper foil for laser processing, and the carrier foil / peeling layer / copper foil for laser processing (difficulty Each layer is laminated like a soluble laser absorption layer / copper foil).
- the copper foil for laser processing with carrier foil since the same configuration as the above-described copper foil for laser processing can be adopted except for the configuration related to the carrier foil, only the configuration related to the carrier foil will be described here.
- Carrier foil is a metal foil that is detachably provided on a copper foil for laser processing.
- the copper foil for laser processing is an ultrathin copper foil having a thickness of 7 ⁇ m or less as described above, By supporting the processing copper foil, it is possible to prevent wrinkles and tears and to improve the handling properties.
- the material constituting the carrier foil is not particularly limited, but it is possible to form the electrolytic copper-tin alloy layer and the copper foil on the carrier foil by electrodeposition through a release layer. It is preferable that it is the metal material which has.
- a copper foil, a copper alloy foil, an aluminum foil, a composite foil in which a metal plating layer such as copper or zinc is provided on the surface of the aluminum foil, a stainless steel foil, a resin film whose surface is metal-coated, or the like can be used.
- a copper foil can be suitably used as a carrier foil.
- the carrier foil can be reused as a copper raw material after being peeled from the laser processing copper foil, and therefore, it is preferable from the viewpoint of resource conservation.
- the thickness of the carrier foil is not particularly limited, but can be, for example, 5 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the carrier foil is less than 5 ⁇ m, the thickness of the carrier foil is thin, and the original purpose of the carrier foil to improve the handling property of the copper foil for ultrathin laser processing having a thickness of 7 ⁇ m or less cannot be achieved, It is not preferable.
- the thickness of the carrier foil is preferably 100 ⁇ m or less, and a thickness of 35 ⁇ m or less is also applicable.
- the copper foil for laser processing with carrier foil is a so-called peelable type copper foil for laser processing with carrier foil.
- the release layer allows the carrier foil to be easily peeled from the copper foil for laser processing by hand, and the adhesive strength between the carrier foil and the copper foil for laser processing is appropriate until the carrier foil is peeled off. It is required to be in close contact.
- the inorganic peeling layer comprised from an inorganic agent and the organic peeling layer comprised from an organic agent are mentioned, for example.
- Inorganic release layer As an inorganic agent constituting the inorganic release layer, for example, one or more selected from chromium, nickel, molybdenum, tantalum, vanadium, tungsten, cobalt, and oxides thereof are mixed and used. be able to.
- Organic release layer As an organic agent constituting the organic release layer, for example, one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids can be mixed and used. .
- the release layer may be either an inorganic release layer or an organic release layer, but is preferably an organic release layer from the viewpoint that the peeling properties of the carrier foil are stabilized.
- the nitrogen-containing organic compound More specifically, it is preferable to employ the following compounds as the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid.
- the nitrogen-containing compound include orthotriazoles, aminotriazoles, imidazoles, salts thereof, and derivatives thereof.
- orthotriazoles such as carboxybenzotriazole, aminotriazoles such as 3-amino-1H-1,2,4-triazole, and triazole derivatives N ′, N′-bis (benzotriazolylmethyl) urea Can be mentioned. Any one or more of these can be used to form an organic release layer composed of a nitrogen-containing compound.
- sulfur-containing compound examples include thiazole, mercaptobenzothiazole, dibenzoazyl disulfide, cyclohexylamine salt of mercaptobenzothiazole, dicyclohexylamine salt of mercaptobenzothiazole, thiocyanuric acid and 2-benzimidazolethiol.
- thiazole mercaptobenzothiazole, dibenzoazyl disulfide
- cyclohexylamine salt of mercaptobenzothiazole dicyclohexylamine salt of mercaptobenzothiazole
- 2-benzimidazolethiol 2-benzimidazolethiol.
- carboxylic acids examples include high molecular weight carboxylic acids.
- high molecular weight carboxylic acids it is particularly preferable to use a fatty acid that is a long-chain hydrocarbon monocarboxylic acid.
- the fatty acid may be a saturated fatty acid, but it is particularly preferable to use an unsaturated fatty acid such as oleic acid or linolenic acid.
- the thickness of the release layer is preferably 100 nm or less, and more preferably 50 nm or less.
- a release layer is provided on the surface of the carrier foil, and copper is deposited on the carrier foil via the release layer by a method such as electrolysis to form an electrolytic copper foil.
- the thickness of the release layer exceeds 100 nm, particularly in the case of an organic release layer, it becomes difficult to form an electrolytic copper foil on the release layer.
- the adhesion strength between the carrier foil and the electrolytic copper foil is lowered. Accordingly, the thickness of the release layer is preferably 100 nm or less.
- the lower limit value of the thickness of the release layer is not particularly limited. However, when the thickness is less than 1 nm, it becomes difficult to form a release layer with a uniform thickness, and the thickness varies. For this reason, it is preferable that the thickness of a peeling layer is 1 nm or more, and it is more preferable that it is 2 nm or more.
- the heat-resistant metal layer The copper foil for laser processing with the carrier foil forms a heat-resistant metal layer between the carrier foil and the release layer, or between the release layer and the electrolytic copper-tin alloy layer of the copper foil for laser processing, It is also preferable to have a layer configuration of carrier foil / heat-resistant metal layer / release layer / copper foil for laser processing or a layer configuration of carrier foil / release layer / heat-resistant metal layer / copper foil for laser processing.
- the manufacturing method of the copper foil for laser processing with a carrier foil is not specifically limited. For example, after forming a release layer on the surface of the carrier foil, the electrolytic copper-tin alloy layer and the copper foil are electrolytically deposited on the carrier foil through the release layer. Any method may be used as long as the foil can be obtained.
- the peeling layer at this time is comprised with the above-mentioned component, it does not affect the measurement of the tin content of the electrolytic copper-tin alloy layer. Therefore, the total copper content is measured using ICP analysis method, fluorescent X-ray apparatus, titration quantitative method, etc. for a solution in which the sample of layer structure of “peeling layer / electrolytic copper-tin alloy layer / copper foil” is completely dissolved. And “the amount of copper contained in the electrolytic copper-tin alloy layer” calculated by subtracting "the amount of copper converted from the cross-sectional thickness of the copper foil” from this total copper content and "the tin content in the solution” From this, the tin content (% by mass) can be calculated.
- the thickness of the copper foil is known in advance by cross-sectional observation, etc., using a fluorescent X-ray film thickness measuring instrument, perform a composition analysis of the foil defined as a two-layer foil, and in the electrolytic copper-tin alloy layer The tin content (% by mass) can be calculated.
- the copper clad laminate according to the present invention will be described.
- the copper foil for laser processing and the insulating layer constituting material are laminated so that the hardly soluble laser absorption layer is disposed on the side irradiated with the infrared laser light. It is characterized by that. That is, the copper-clad laminate according to the present invention is formed by laminating the insulating layer constituent material and the copper foil for laser processing, and the insulating layer constituent material / copper foil / slightly soluble laser absorbing layer (electrolytic copper-tin alloy layer). Any structure may be used as long as it has a layer structure stacked in the order of).
- the said copper clad laminated body can be obtained, there will be no limitation in particular in the manufacturing method.
- the copper foil side of the copper foil for laser processing or the copper foil with carrier foil is laminated on the insulating resin base material or insulating resin layer of the so-called B stage, and heated and pressed on the insulating resin base material or insulating resin layer.
- a copper clad laminate in which a copper foil for laser processing is laminated can be obtained.
- the carrier foil may be removed at an appropriate stage.
- the copper foil 10 for laser processing used here has a layer structure of primer resin layer 11 / copper foil (electrolytic copper foil layer) 12 / electrolytic copper-tin alloy layer 13 (slightly soluble laser absorbing layer), It is assumed that no roughening treatment layer is provided on the bonding surface of the copper foil 12.
- a method for manufacturing a multilayer printed wiring board in which three or more wiring layers are laminated via an insulating layer will be described.
- the method for producing a printed wiring board according to the present invention is not limited to the method for producing a multilayer printed wiring board, and can also be applied when producing a double-sided printed wiring board.
- the bonding surface side of the copper foil 10 for laser processing with a carrier foil is laminated on the bonding surface via a so-called B-stage insulating layer constituting material 20.
- the laminated body shown to Fig.2 (a) is obtained by closely_contact
- the surface of the electrolytic copper-tin alloy layer 13 which is the outermost layer is directly irradiated with infrared laser light by a carbon dioxide laser or the like to form the micro via hole 40 having the conductor pattern portion 30a of the inner layer circuit 30 as the bottom (FIG. 2 (b)).
- a desmear process for removing smear remaining at the bottom of the micro via hole 40 using a desmear liquid is performed (see FIG. 2C).
- the desmear process after immersing the laminate 100 in a swelling solution, the laminate 100 is immersed in a so-called desmear solution (for example, an alkaline permanganate aqueous solution) to remove smear, and then immersed in a neutralization solution (reducing agent).
- desmear solution for example, an alkaline permanganate aqueous solution
- a neutralization solution reducing agent
- a microetching process is performed as a pretreatment for the electroless plating process.
- the splash and the like attached around the micro via hole 40 is removed using a microetching solution (for example, sulfuric acid-hydrogen peroxide etchant or ammonium persulfate aqueous solution). If smear remains at the bottom of the micro via hole 40, it is removed (see FIG. 2D).
- the surface of the laminate 100 comes into contact with a processing solution having etching properties with respect to copper, such as a neutralizing solution and a microetching solution. Since the electrolytic copper-tin alloy layer 13 has an etching property with respect to the copper etching solution, the surface thereof is etched in these steps. Since the etching rate with respect to the copper etching solution varies depending on the thickness and tin content of the electrolytic copper-tin alloy layer 13, the timing for dissolving the electrolytic copper-tin alloy layer 13 can be controlled by adjusting these. it can.
- the electrolytic copper-tin is used in the desmear process by adjusting the thickness and material of the electrolytic copper-tin alloy layer 13. It is preferable to completely dissolve and remove the alloy layer 13.
- the electrolytic copper-tin alloy layer 13 is left without being completely dissolved in the desmear process, and in the subsequent microetching process.
- the electrolytic copper-tin alloy layer 13 may be completely dissolved and removed.
- the timing for dissolving and removing the electrolytic copper-tin alloy layer 13 may be set appropriately according to the characteristics required for the printed wiring board.
- an electroless plating film is formed on the inside of the micro via hole 40 and on the copper foil layer 12 to perform interlayer connection (not shown).
- a plating resist is provided on the seed layer (copper foil + electroless plating film), a wiring pattern is formed by an electrolytic plating method, and the via hole is filled and plated.
- the seed layer under the plating resist is removed together with the plating resist by flash etching.
- the steps after the electroless plating step are not shown.
- the reference numerals for the respective constituent elements are omitted.
- the copper foil for laser processing it is possible to directly irradiate the laser beam without performing pretreatment for increasing the absorption rate of the laser beam such as blackening treatment. Processing can be performed. For this reason, the frequency
- an electrolytic copper-tin alloy layer is used as the poorly soluble laser absorption layer, by adjusting the tin content and the thickness of the electrolytic copper-tin alloy layer as appropriate, The timing for dissolving and removing the tin alloy layer can be controlled.
- FIG. 2 the case where the tin content in the electrolytic copper-tin alloy layer is relatively large and the electrolytic copper-tin layer is not dissolved in the desmear process is shown.
- the present invention is not limited to the illustrated example, and the electrolytic copper-tin alloy is adjusted in the desmear process by adjusting the amount and thickness of tin in the electrolytic copper-tin alloy layer according to the characteristics required for the printed wiring board. The layer may be removed by dissolution.
- a copper foil for carrier foil laser processing is prepared by the method described below, and then a copper-clad laminate is manufactured, and laser hole drilling processability evaluation using a carbon dioxide gas laser is performed, and a printed wiring board manufacturing process is performed.
- the evaluation of the variation in the thickness of the copper foil (electrolytic copper foil layer) when subjected to the etching treatment performed before forming the wiring pattern was performed. Hereinafter, it will be described in order. The evaluation method will be described later.
- Step A An electrolytic copper foil having a surface roughness (Rzjis) on one side of 0.6 ⁇ m and a thickness of 18 ⁇ m was used as a carrier foil, and a release layer was formed on the surface of the carrier foil as follows.
- the surface roughness (Rzjis) is a value measured with a stylus type surface roughness meter using a diamond stylus having a tip radius of curvature of 2 ⁇ m in accordance with JIS B 0601.
- This carrier foil was immersed in a dilute sulfuric acid aqueous solution containing carboxybenzotriazole having a free sulfuric acid concentration of 150 g / l, a copper concentration of 10 g / l, a carboxybenzotriazole concentration of 800 ppm, and a liquid temperature of 30 ° C. for 30 seconds. Then, by picking up the carrier foil, the contaminated components adhering to the surface of the carrier foil are pickled and removed, and carboxybenzotriazole is adsorbed on the surface to form a release layer on the surface of the carrier foil.
- the carrier foil provided.
- Step B Next, in the metal component-containing electrolyte, the carrier foil provided with the release layer is cathode-polarized to form a heat-resistant metal layer on the surface of the release layer, and the carrier foil provided with the heat-resistant metal layer and the release layer; did.
- nickel electrolyte nickel sulfate (NiSO 4 ⁇ 6H 2 O) and 330 g / l, nickel chloride (NiCl 2 ⁇ 6H 2 O) and 45 g / l, containing boric acid 30 g / l
- the bath pH is 3 A watt bath, electrolysis at a liquid temperature of 45 ° C.
- a nickel layer having a thickness of 0.01 ⁇ m is formed on the surface of the release layer, and a carrier having a heat-resistant metal layer and a release layer A foil was prepared.
- Step C Next, in a copper-tin plating bath having the following composition, a carrier foil comprising the refractory metal layer and a release layer is cathodically polarized under the following electrolysis conditions, and a thickness of 0.7 ⁇ m is formed on the surface of the refractory metal layer. An electrolytic copper-tin alloy layer was formed.
- Step D Next, a carrier foil provided with an electrolytic copper-tin alloy layer and the like is cathodic polarized in a copper plating bath having the following composition under the following conditions, and an electrolytic copper foil having a thickness of 2 ⁇ m on the surface of the electrolytic copper-tin metal layer.
- the copper foil for laser processing with a carrier foil which concerns on this invention was obtained.
- Step E In this example, a zinc-nickel alloy rust preventive layer is further formed on the surface of the copper foil for laser processing with a carrier foil on the side of the electrolytic copper foil, and subjected to electrolytic chromate treatment and amino silane coupling agent treatment.
- the copper foil for surface treatment laser processing with a carrier foil was obtained.
- the tin content in the electrolytic copper-tin alloy layer was 27.5% by mass.
- the tin content in the examples was measured as follows. An electrolytic copper-tin alloy layer is formed at a stage where a release layer is formed on the surface of the carrier foil, a heat-resistant metal layer is formed on the surface of the release layer, and an electrolytic copper-tin alloy layer is formed on the surface of the heat-resistant metal layer. A tin content measurement sample was used. Thereafter, the electrolytic copper-tin alloy layer of the sample is peeled from the carrier foil, and the composition analysis of the foil is performed using a fluorescent X-ray film thickness measuring device XDAL-FD (manufactured by Fisher Instruments). The tin content (% by mass) was calculated. In the following comparative examples, the tin content is measured by the same method.
- Comparative Example 1 In Comparative Example 1, a peelable type electrolytic copper foil with a carrier foil was produced in the same manner as in the Example except that the electrolytic copper-tin alloy layer was not provided. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
- Comparative Example 2 In Comparative Example 2, in Step C, the carrier foil was cathodically polarized under the following electrolysis conditions in a copper-tin plating bath having the following composition, and the thickness of 0.7 ⁇ m was interposed on the carrier foil with a release layer and a heat-resistant metal layer.
- An electrolytic copper foil with a carrier foil was produced in the same manner as in Example except that the electrolytic copper-tin alloy layer was formed. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
- the tin content in the electrolytic copper-tin alloy layer was 12.9% by mass.
- Comparative Example 3 In Comparative Example 3, using the electrolytic copper foil with carrier foil of Comparative Example 1, a copper clad laminate was produced in the same manner as in the example. Then, a metal tin layer having a thickness of 0.4 ⁇ m was formed on the surface of the copper foil of the copper clad laminate using a commercially available electroless tin plating solution. Then, the copper clad laminate on which the metal tin layer is formed is heat-treated at 200 ° C. for 30 minutes to cause mutual diffusion between the copper component of the electrolytic copper foil and the tin component of the metal tin layer, A copper-clad laminate having a diffusion alloy layer mainly composed of tin-copper on the surface layer of the copper foil was obtained.
- Desmear process First, in the desmear process, swelling treatment (swelling solution: Rohm & Haas, MLB-211, liquid temperature: 75 ° C., treatment time: 15 minutes), oxidation treatment with an alkaline aqueous solution of potassium permanganate (oxidation treatment solution: Each treatment of Rohm & Haas, MLB-213, liquid temperature: 80 ° C., treatment time: 15 minutes, neutralization treatment (neutralization treatment liquid: Rohm & Haas, MLB-216, liquid temperature: 40 ° C., treatment time: 15 minutes) After that, after washing and drying, the thickness was measured by cross-sectional observation.
- swelling treatment swelling solution: Rohm & Haas, MLB-211, liquid temperature: 75 ° C., treatment time: 15 minutes
- oxidation treatment with an alkaline aqueous solution of potassium permanganate oxidation treatment solution: Each treatment of Rohm & Haas, MLB-213, liquid temperature: 80 ° C., treatment time: 15 minutes
- neutralization treatment neutral
- Micro-etching process Next, in the micro-etching process, each copper clad laminate after the desmear process is immersed in a sulfuric acid-hydrogen peroxide etching solution (CPE800 manufactured by Mitsubishi Gas Chemical Co., Ltd.) at a liquid temperature of 30 ° C. for 60 seconds. After washing with water and drying, the thickness was measured by cross-sectional observation. For cross-sectional observation, VE-9800 manufactured by Keyence Corporation was used.
- CPE800 sulfuric acid-hydrogen peroxide etching solution
- Table 1 shows the top diameter when via holes are formed under the above processing conditions for each copper-clad laminate.
- the top diameter refers to the opening diameter of the via hole as shown in FIG.
- the electrolytic copper-tin alloy layer containing tin is the outermost layer, and this electrolytic copper-tin alloy layer
- drilling was possible by laser processing without performing pretreatment for increasing the absorption rate of laser light such as blackening treatment.
- the copper-clad laminate produced in Comparative Example 1 cannot be directly drilled by laser processing, and if no pretreatment for increasing the laser light absorption rate, such as blackening treatment, is performed, the laser It was confirmed that micro via holes cannot be formed by processing.
- the electrolytic copper foil of Comparative Example 3 includes a diffusion alloy layer obtained by interdiffusing copper and tin with a metal tin layer formed by electroless plating on the surface thereof by thermal diffusion.
- the diffusion alloy layer the distribution of tin in the thickness direction is nonuniform, and the closer to the surface, the greater the distribution of tin.
- FIG. 3 shows FIB-SIM images showing cross sections of the copper clad laminates of Example and Comparative Example 1.
- the copper clad laminate produced in the example is provided with a 0.7 ⁇ m electrolytic copper-tin alloy layer on a 2 ⁇ m thick electrolytic copper foil layer.
- the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.21 ⁇ m.
- the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.38 ⁇ m.
- the presence of the electrolytic copper-tin alloy layer does not change the thickness of the copper foil, and the initial The thickness (2 ⁇ m) can be maintained.
- the copper clad laminate produced in Comparative Example 1 does not have an electrolytic copper-tin alloy layer on the electrolytic copper foil layer, so that it is 0.10 ⁇ m in the desmear process, and in the microetching process.
- the thickness is reduced to 1.03 ⁇ m.
- the tin content in the electrolytic copper-tin alloy layer is 27.5% by mass, and as shown in FIG. 1, the etching rate is slower than that of the electrolytic copper foil not containing tin.
- the amount of etchings also becomes large and there exists a possibility that variation may arise in the thickness of copper foil.
- the copper clad laminate of Comparative Example 2 includes an electrolytic copper-tin alloy layer having a tin content of 12.9% by mass, and as shown in FIG.
- the etching rate of the layer is faster than that of the electrolytic copper foil containing no tin. Therefore, the copper-clad laminate of Comparative Example 2 has an electrolytic copper-tin alloy layer on the surface of the electrolytic copper foil layer, but the etching amount in the desmear process is 0.20 ⁇ m, and the etching amount in the microetching process is 1.25 ⁇ m. Also in this case, the surface of the electrolytic copper foil layer is dissolved, and the thickness of the electrolytic copper foil layer may vary.
- the diffusion alloy layer mainly composed of tin-copper has a two-layer structure of a tin layer and a tin-copper diffusion alloy layer as described above. And the etching rate with respect to each etching liquid differs in a tin copper diffusion alloy layer, respectively. In particular, it is difficult to dissolve the metal tin layer as the outermost layer with a general etching treatment liquid for copper foil (see FIG. 1).
- the total amount of etching after the desmear process and the micro-etching process is as small as 0.05 ⁇ m and functions as an etching resist layer, but the seed layer is removed by etching in the subsequent flash etching process after the wiring pattern is formed.
- the said copper foil it thinks that an etching rate differs in each layer of a metal tin layer, a tin copper diffusion alloy layer, and an electrolytic copper foil layer, and it becomes difficult to etch uniformly in the thickness direction.
- the etching rate of the wiring pattern portion formed by electrolytic copper plating is higher than that of the metal tin layer that is the outermost layer. Therefore, the etching factor is reduced, and it becomes difficult to form a wiring pattern with a good line width.
- the electrolytic copper-tin alloy layer can be dissolved and removed in the desmear process and the microetching process. What is necessary is just to remove the layer and the electroless copper plating film formed on this electrolytic copper foil layer. Since these are all copper layers, there is no significant difference in the etching rate. Further, no great difference appears with the etching rate of the wiring pattern portion formed by electrolytic copper plating. Therefore, according to the copper foil for laser processing according to the present invention, it is possible to form a wiring pattern with a good etching factor.
- the laser processability is excellent, and a uniform etching rate in the thickness direction can be obtained in the subsequent etching process.
- the electrolytic copper-tin alloy layer can function as an etching resist, it is possible to prevent the copper foil surface from being melted and causing variations in the thickness of the copper foil in various etching processes before forming the wiring pattern. it can. Further, when removing the seed layer, only the copper foil portion needs to be dissolved and removed, so that a wiring pattern can be formed with a good etching factor.
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Abstract
Description
本件発明に係るレーザー加工用銅箔は、銅エッチング液に対するエッチング性を有すると共に、そのエッチング速度が銅箔よりも遅く、且つ、赤外線レーザー光を吸収する難溶性レーザー吸収層を銅箔の表面に備えたことを特徴とする。本件発明に係るレーザー加工用銅箔は、プリント配線板の製造工程において、Cuダイレクト法により、黒化処理等の前処理を施すことなく、レーザー加工用銅箔の表面に対して、レーザー光を直接照射して、マイクロビアホール等の微細孔をレーザー加工により形成可能にしたものである。 1. Copper foil for laser processing The copper foil for laser processing according to the present invention has an etching property with respect to a copper etching solution, an etching rate that is slower than that of the copper foil, and a hardly soluble laser absorbing layer that absorbs infrared laser light. It is provided on the surface of the copper foil. The copper foil for laser processing according to the present invention provides laser light to the surface of the copper foil for laser processing without performing pretreatment such as blackening treatment by the Cu direct method in the manufacturing process of the printed wiring board. By direct irradiation, micro holes such as micro via holes can be formed by laser processing.
まず、電解銅-スズ合金層について説明する。スズは銅と比較すると、遠赤外線~赤外線波長域の波長を有するレーザー光(炭酸ガスレーザー光等)の吸収率が高い。つまり、当該電解銅-スズ合金層をレーザー光吸収層として機能させることができ、上述のとおり、Cuダイレクト法により孔開け加工する際の前処理を不要とすることができる。また、本件発明において、電解銅-スズ合金層は、孔開け加工後、配線パターン形成前に行われるデスミア工程やマイクロエッチング工程等で行われる各種エッチング処理において、銅箔の表面がエッチングされるのを防止するためのエッチングレジスト層としても機能させることができる。当該電解銅-スズ合金層は、これらの配線パターン形成前に行われる各種エッチング処理においてエッチングされる。しかしながら、当該電解銅-スズ合金層が溶解除去されるタイミングは、そのスズ含有量や厚みによって制御することができる。このため、層間接続のための無電解めっき工程の前段階までの間に、銅箔の表面を溶解させることなく、電解銅-スズ合金層のみを溶解除去することも可能になる。従って、例えば、MSAP法により配線パターンを形成する場合には、当初の厚みを維持した状態の銅箔上に無電解めっき被膜を形成することができ、均一な厚みのシード層を得ることができる。 1-1. Electrolytic copper-tin alloy layer First, the electrolytic copper-tin alloy layer will be described. Tin has a higher absorption rate of laser light (carbon dioxide laser light, etc.) having a wavelength in the far-infrared to infrared wavelength range compared to copper. That is, the electrolytic copper-tin alloy layer can function as a laser light absorption layer, and as described above, the pretreatment at the time of drilling by the Cu direct method can be eliminated. In the present invention, the electrolytic copper-tin alloy layer is etched on the surface of the copper foil in various etching processes performed in a desmear process, a micro-etching process, etc. performed after drilling and before forming a wiring pattern. It can also function as an etching resist layer for preventing the above. The electrolytic copper-tin alloy layer is etched in various etching processes performed before these wiring patterns are formed. However, the timing at which the electrolytic copper-tin alloy layer is dissolved and removed can be controlled by its tin content and thickness. Therefore, it is possible to dissolve and remove only the electrolytic copper-tin alloy layer without dissolving the surface of the copper foil before the electroless plating step for interlayer connection. Therefore, for example, when a wiring pattern is formed by the MSAP method, an electroless plating film can be formed on a copper foil in which the original thickness is maintained, and a seed layer having a uniform thickness can be obtained. .
本件発明において、難溶性レーザー吸収層として電解銅-スズ合金層を用いる場合、当該電解銅-スズ合金層中のスズ含有量を25質量%以上とするのは、上述したエッチングレジストとしての機能を発揮させるためである。図1に示すように、電解銅-スズ合金層中のスズ含有量が25質量%未満の場合、電解銅-スズ合金層のエッチング速度は、スズ含有量が0質量%の電解銅箔と比較すると速くなる。一方、電解銅-スズ合金層中のスズ含有量が25質量%以上になると、そのエッチング速度はスズを含有しない通常の電解銅箔と比較すると遅くなる。従って、当該電解銅-スズ合金層中のスズ含有量を25質量%以上とすることにより、上述のとおり、電解銅-スズ合金層をエッチングレジストとして機能させることができ、上記配線パターン形成前に行われる各種エッチング処理の際に、銅箔が溶解して、銅箔の厚みにバラツキが生じるのを防止することができる。なお、この明細書は、銅-スズ合金層中の銅とスズの合計含有量を100質量%としたときの特定のスズ質量%に関する発明について記載している。 (1) Tin content In the present invention, when an electrolytic copper-tin alloy layer is used as the hardly soluble laser absorption layer, the tin content in the electrolytic copper-tin alloy layer is 25% by mass or more as described above. This is because the function as an etching resist is exhibited. As shown in FIG. 1, when the tin content in the electrolytic copper-tin alloy layer is less than 25% by mass, the etching rate of the electrolytic copper-tin alloy layer is compared with that of the electrolytic copper foil having a tin content of 0% by mass. Then it will be faster. On the other hand, when the tin content in the electrolytic copper-tin alloy layer is 25% by mass or more, the etching rate is slow as compared with a normal electrolytic copper foil containing no tin. Therefore, by setting the tin content in the electrolytic copper-tin alloy layer to 25% by mass or more, as described above, the electrolytic copper-tin alloy layer can function as an etching resist, and before the wiring pattern is formed, It is possible to prevent the copper foil from being melted and causing variations in the thickness of the copper foil during various etching processes to be performed. This specification describes an invention relating to specific tin mass% when the total content of copper and tin in the copper-tin alloy layer is 100 mass%.
電解銅-スズ合金層の厚みは、当該レーザー加工用銅箔の厚み及び用途に応じて適宜、適切な値とすることができる。しかしながら、当該電解銅-スズ合金層を配線パターン形成前の適切な段階でエッチングにより溶解除去すること等を考慮すると、3μm以下であることが好ましく、2μm以下であることがより好ましい。一方、当該電解銅-スズ合金層の厚みが0.1μm未満になると、レーザー光の吸収率を向上するという目的を達成することが困難になると共に、配線パターン形成前に行われる各種エッチング処理において当該電解銅-スズ合金層を銅箔のエッチングレジストとして十分機能させることができなくなる場合がある。従って、当該観点から電解銅-スズ合金層の厚みは、0.3μm以上であることが好ましく、0.5μm以上であることがより好ましい。また、上述したとおり、銅エッチング液に対するエッチング速度は当該電解銅-スズ合金層中のスズ含有量によって変化するから、当該電解銅-スズ合金層の厚みはそのスズ含有量に応じて、適宜、適切な値とすることが好ましい。 (3) Thickness of the electrolytic copper-tin alloy layer The thickness of the electrolytic copper-tin alloy layer can be set to an appropriate value depending on the thickness and use of the laser processing copper foil. However, in consideration of dissolving and removing the electrolytic copper-tin alloy layer by etching at an appropriate stage before forming the wiring pattern, it is preferably 3 μm or less, and more preferably 2 μm or less. On the other hand, if the thickness of the electrolytic copper-tin alloy layer is less than 0.1 μm, it is difficult to achieve the purpose of improving the absorption rate of the laser beam, and in various etching processes performed before forming the wiring pattern. In some cases, the electrolytic copper-tin alloy layer cannot function sufficiently as an etching resist for copper foil. Therefore, from this viewpoint, the thickness of the electrolytic copper-tin alloy layer is preferably 0.3 μm or more, and more preferably 0.5 μm or more. In addition, as described above, the etching rate for the copper etching solution varies depending on the tin content in the electrolytic copper-tin alloy layer. Therefore, the thickness of the electrolytic copper-tin alloy layer is appropriately determined according to the tin content. An appropriate value is preferable.
本件発明において、銅エッチング液としては、銅に対するエッチング液として一般に使用されているエッチング液であれば、特に限定することなく用いることができる。例えば、塩化銅系エッチング液、塩化鉄系エッチング液、硫酸-過酸化水素水系エッチング液、過硫酸ナトリウム系エッチング液、過硫酸アンモニウム系エッチング液、過硫酸カリウム系エッチング液等、各種の銅エッチング液を用いることができる。 (4) Copper etchant In the present invention, any copper etchant can be used without particular limitation as long as it is an etchant generally used as an etchant for copper. For example, various copper etching solutions such as copper chloride etching solution, iron chloride etching solution, sulfuric acid-hydrogen peroxide etching solution, sodium persulfate etching solution, ammonium persulfate etching solution, potassium persulfate etching solution, etc. Can be used.
次に、銅箔について説明する。本件発明において、銅箔とは銅の含有量が99質量%以上の金属箔をいい、不可避不純物を除いてスズを含有しないスズ非含有銅箔を指す。当該銅箔は、電解銅箔及び圧延銅箔のいずれであってもよい。しかしながら、経済性及び生産効率を考慮すると、電解銅箔であることがより好ましい。 1-2. Copper foil Next, copper foil is demonstrated. In the present invention, the copper foil refers to a metal foil having a copper content of 99% by mass or more, and refers to a tin-free copper foil that does not contain tin except for inevitable impurities. The copper foil may be either an electrolytic copper foil or a rolled copper foil. However, in view of economy and production efficiency, an electrolytic copper foil is more preferable.
本件発明に係るレーザー加工用銅箔において、銅箔の接着面、すなわち、上記電解銅-スズ合金層が設けられる面とは反対側の面に粗化処理層が設けられていてもよい。銅箔の接着面に粗化処理層を設けることにより、銅箔と絶縁層との密着性を向上させることができる。粗化処理層は、銅箔の表面(接着面)に微細金属粒を付着形成させる方法、エッチング法で粗化表面を形成する方法等により形成することができる。粗化処理層を形成するための方法は、銅箔と絶縁層との密着性を物理的に向上することができればどのような方法で行ってもよく、従来公知の粗化処理に関する種々の方法を採用することができる。 1-3. Roughening treatment layer In the laser processing copper foil according to the present invention, a roughening treatment layer is provided on the adhesive surface of the copper foil, that is, the surface opposite to the surface on which the electrolytic copper-tin alloy layer is provided. Also good. By providing the roughening treatment layer on the bonding surface of the copper foil, the adhesion between the copper foil and the insulating layer can be improved. The roughening treatment layer can be formed by a method of depositing and forming fine metal particles on the surface (bonding surface) of the copper foil, a method of forming a roughened surface by an etching method, or the like. The method for forming the roughened layer may be any method as long as the adhesion between the copper foil and the insulating layer can be physically improved. Can be adopted.
本件発明に係るレーザー加工用銅箔において、銅箔の上記接着面に、プライマー樹脂層が設けられていてもよい。本件発明において、プライマー樹脂層とは、銅箔と絶縁層構成材料との双方に対して良好な密着性を有する接着剤層である。例えば、プライマー樹脂層として、エポキシ樹脂、芳香族ポリアミド樹脂を含有する樹脂組成物からなる層とすることができる。当該プライマー樹脂層を銅箔の接着面に設けることにより、銅箔を絶縁層構成材料と良好に密着させることができる。 1-4. Primer resin layer In the copper foil for laser processing according to the present invention, a primer resin layer may be provided on the adhesive surface of the copper foil. In the present invention, the primer resin layer is an adhesive layer having good adhesion to both the copper foil and the insulating layer constituting material. For example, the primer resin layer can be a layer made of a resin composition containing an epoxy resin or an aromatic polyamide resin. By providing the primer resin layer on the adhesive surface of the copper foil, the copper foil can be satisfactorily adhered to the insulating layer constituting material.
本件発明に係るレーザー加工用銅箔において、難溶性レーザー吸収層が上述の電解銅-スズ合金層である場合、例えば、銅イオンとスズイオンとを含む電解液を用い、上記銅箔上に電解めっき法によりスズ含有量が25質量%以上50質量%以下の電解銅-スズ合金層を積層したレーザー加工用銅箔を得ることができれば、その製造方法は特に限定されるものではない。また、銅箔の接着面には上述した粗化処理層、プライマー樹脂層の他、防錆処理層、シランカップリング処理層等、必要に応じて各種表面処理層を設けてもよいのは勿論である。 1-5. Manufacturing method of copper foil for laser processing In the copper foil for laser processing according to the present invention, when the hardly soluble laser absorbing layer is the above-mentioned electrolytic copper-tin alloy layer, for example, an electrolytic solution containing copper ions and tin ions is used. If the copper foil for laser processing can be obtained by laminating an electrolytic copper-tin alloy layer having a tin content of 25 mass% or more and 50 mass% or less on the copper foil by an electrolytic plating method, its production method is particularly limited. It is not something. In addition to the roughening treatment layer and primer resin layer described above, various surface treatment layers such as a rust prevention treatment layer and a silane coupling treatment layer may be provided on the adhesive surface of the copper foil as required. It is.
次に、本件発明に係るキャリア箔付のレーザー加工用銅箔(以下、キャリア箔付レーザー加工用銅箔)について説明する。当該キャリア箔付レーザー加工用銅箔は、上記レーザー加工用銅箔の難溶性レーザー吸収層上にキャリア箔を剥離可能に備えたものであり、キャリア箔/剥離層/レーザー加工用銅箔(難溶性レーザー吸収層/銅箔)のように各層が積層されたものである。当該キャリア箔付レーザー加工用銅箔において、キャリア箔に関する構成以外は、上述したレーザー加工用銅箔と同じ構成を採用することができるため、ここではキャリア箔に関する構成についてのみ説明する。 2. Next, the copper foil for laser processing with carrier foil according to the present invention (hereinafter, copper foil for laser processing with carrier foil) according to the present invention will be described. The copper foil for laser processing with carrier foil is provided with the carrier foil peelable on the hardly soluble laser absorbing layer of the copper foil for laser processing, and the carrier foil / peeling layer / copper foil for laser processing (difficulty Each layer is laminated like a soluble laser absorption layer / copper foil). In the copper foil for laser processing with carrier foil, since the same configuration as the above-described copper foil for laser processing can be adopted except for the configuration related to the carrier foil, only the configuration related to the carrier foil will be described here.
キャリア箔は、レーザー加工用銅箔に剥離可能に設けられた金属箔であり、レーザー加工用銅箔が上述したように7μm以下の厚みの極薄銅箔である場合、キャリア箔によりレーザー加工用銅箔を支持することにより、シワや破れなどを防止し、そのハンドリング性を向上することができる。キャリア箔を構成する材料は、特に限定されるものではないが、キャリア箔上に剥離層を介して電析によって、上記電解銅-スズ合金層及び銅箔を形成可能とするため、導電性を有する金属材料であることが好ましい。例えば、銅箔、銅合金箔、アルミニウム箔、アルミニウム箔の表面に銅或いは亜鉛等の金属めっき層が設けられた複合箔、ステンレス箔、表面をメタルコーティングした樹脂フィルム等を用いることができる。これらの材料の中でも、銅箔をキャリア箔として好適に用いることができる。銅箔をキャリア箔として用いることにより、レーザー加工用銅箔からキャリア箔を剥離した後、これを銅原料として再利用することができるため、資源保全の観点から好ましい。 2-1. Carrier foil Carrier foil is a metal foil that is detachably provided on a copper foil for laser processing. When the copper foil for laser processing is an ultrathin copper foil having a thickness of 7 μm or less as described above, By supporting the processing copper foil, it is possible to prevent wrinkles and tears and to improve the handling properties. The material constituting the carrier foil is not particularly limited, but it is possible to form the electrolytic copper-tin alloy layer and the copper foil on the carrier foil by electrodeposition through a release layer. It is preferable that it is the metal material which has. For example, a copper foil, a copper alloy foil, an aluminum foil, a composite foil in which a metal plating layer such as copper or zinc is provided on the surface of the aluminum foil, a stainless steel foil, a resin film whose surface is metal-coated, or the like can be used. Among these materials, a copper foil can be suitably used as a carrier foil. By using the copper foil as the carrier foil, the carrier foil can be reused as a copper raw material after being peeled from the laser processing copper foil, and therefore, it is preferable from the viewpoint of resource conservation.
当該キャリア箔付レーザー加工用銅箔は、いわゆるピーラブルタイプのキャリア箔付レーザー加工用銅箔である。剥離層には、キャリア箔をレーザー加工用銅箔に対して手作業で簡易に剥離可能にすると共に、キャリア箔が剥離されるまでの間はキャリア箔とレーザー加工用銅箔に適度な密着強度で密着させることが要求される。このような剥離層として、例えば、無機剤から構成される無機剥離層、有機剤から構成される有機剥離層が挙げられる。 2-2. Release Layer The copper foil for laser processing with carrier foil is a so-called peelable type copper foil for laser processing with carrier foil. The release layer allows the carrier foil to be easily peeled from the copper foil for laser processing by hand, and the adhesive strength between the carrier foil and the copper foil for laser processing is appropriate until the carrier foil is peeled off. It is required to be in close contact. As such a peeling layer, the inorganic peeling layer comprised from an inorganic agent and the organic peeling layer comprised from an organic agent are mentioned, for example.
無機剥離層を構成する無機剤として、例えば、クロム、ニッケル、モリブデン、タンタル、バナジウム、タングステン、コバルト及びこれらの酸化物から選ばれる1種又は2種以上を混合して用いることができる。 (1) Inorganic release layer As an inorganic agent constituting the inorganic release layer, for example, one or more selected from chromium, nickel, molybdenum, tantalum, vanadium, tungsten, cobalt, and oxides thereof are mixed and used. be able to.
有機剥離層を構成する有機剤として、例えば、窒素含有有機化合物、硫黄含有有機化合物、カルボン酸の中から選択される1種又は2種以上を混合して用いることができる。剥離層は無機剥離層及び有機剥離層のいずれであってもよいが、キャリア箔の引き剥がし特性が安定するという観点から有機剥離層であることが好ましい。 (2) Organic release layer As an organic agent constituting the organic release layer, for example, one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids can be mixed and used. . The release layer may be either an inorganic release layer or an organic release layer, but is preferably an organic release layer from the viewpoint that the peeling properties of the carrier foil are stabilized.
剥離層の厚みは、100nm以下であることが好ましく、50nm以下であることがより好ましい。いわゆるピーラブルタイプのキャリア箔付銅箔では、一般に、キャリア箔の表面に剥離層を設け、電解等の手法により、剥離層を介してキャリア箔上に銅を析出させて電解銅箔を形成する。このとき、剥離層の厚みが100nmを超えると、特に有機系剥離層の場合、当該剥離層上に電解銅箔を形成することが困難になる。また、これと同時に、キャリア箔と電解銅箔との密着強度が低下する。従って、剥離層の厚みは100nm以下であることが好ましい。均一な厚みの剥離層を形成することができれば、剥離層の厚みの下限値は特に限定されるものではない。しかしながら、1nm未満になると、均一な厚みで剥離層を形成することが困難になり、厚みにバラツキが生じるようになる。このため、剥離層の厚みは1nm以上であることが好ましく、2nm以上であることがより好ましい。 (3) Thickness of release layer The thickness of the release layer is preferably 100 nm or less, and more preferably 50 nm or less. In the so-called peelable copper foil with carrier foil, generally, a release layer is provided on the surface of the carrier foil, and copper is deposited on the carrier foil via the release layer by a method such as electrolysis to form an electrolytic copper foil. . At this time, when the thickness of the release layer exceeds 100 nm, particularly in the case of an organic release layer, it becomes difficult to form an electrolytic copper foil on the release layer. At the same time, the adhesion strength between the carrier foil and the electrolytic copper foil is lowered. Accordingly, the thickness of the release layer is preferably 100 nm or less. If the release layer having a uniform thickness can be formed, the lower limit value of the thickness of the release layer is not particularly limited. However, when the thickness is less than 1 nm, it becomes difficult to form a release layer with a uniform thickness, and the thickness varies. For this reason, it is preferable that the thickness of a peeling layer is 1 nm or more, and it is more preferable that it is 2 nm or more.
当該キャリア箔付レーザー加工用銅箔は、キャリア箔と剥離層の間、若しくは、剥離層とレーザー加工用銅箔の電解銅-スズ合金層との間に耐熱金属層を形成し、キャリア箔/耐熱金属層/剥離層/レーザー加工用銅箔の層構成、若しくは、キャリア箔/剥離層/耐熱金属層/レーザー加工用銅箔の層構成とすることも好ましい。 2-3. The heat-resistant metal layer The copper foil for laser processing with the carrier foil forms a heat-resistant metal layer between the carrier foil and the release layer, or between the release layer and the electrolytic copper-tin alloy layer of the copper foil for laser processing, It is also preferable to have a layer configuration of carrier foil / heat-resistant metal layer / release layer / copper foil for laser processing or a layer configuration of carrier foil / release layer / heat-resistant metal layer / copper foil for laser processing.
キャリア箔付レーザー加工用銅箔の製造方法は特に限定されるものではない。例えば、キャリア箔の表面に剥離層を形成した後、剥離層を介してキャリア箔上に上記電解銅-スズ合金層、銅箔を電解析出させる等、上記構成のキャリア箔付レーザー加工用銅箔を得ることができればどのような方法で製造してもよい。 2-4. The manufacturing method of the copper foil for laser processing with a carrier foil The manufacturing method of the copper foil for laser processing with a carrier foil is not specifically limited. For example, after forming a release layer on the surface of the carrier foil, the electrolytic copper-tin alloy layer and the copper foil are electrolytically deposited on the carrier foil through the release layer. Any method may be used as long as the foil can be obtained.
キャリア箔付レーザー加工用銅箔の場合、「キャリア箔/剥離層/電解銅-スズ合金層/銅箔」の層構成を備えている。従って、電解銅-スズ合金層のスズ含有量の測定を行うためには、以下のような方法を採用することが好ましい。本件出願に係るキャリア箔付レーザー加工用銅箔の場合、キャリア箔を引き剥がすと「剥離層/電解銅-スズ合金層/銅箔」の層構成になる。そして、このときの剥離層は、上述の成分で構成されているため、電解銅-スズ合金層のスズ含有量の測定に影響を及ぼすものではない。よって、「剥離層/電解銅-スズ合金層/銅箔」の層構成の試料を全溶解した溶液を、ICP分析法、蛍光X線装置、滴定定量法等を用いて全銅含有量を測定し、この全銅含有量から「銅箔の断面厚さから換算した銅量」を差し引くことで算出した「電解銅-スズ合金層に含まれる銅量」と「溶解液中のスズ含有量」とからスズ含有量(質量%)を算出できる。また、あらかじめ断面観察などにより銅箔の厚みがわかっている場合は、蛍光X線膜厚測定器を用いて、二層箔として定義した箔の組成分析を行い、電解銅―スズ合金層中のスズ含有量(質量%)を算出できる。 2-5. Measuring method of tin content of electrolytic copper-tin alloy layer of copper foil for laser processing with carrier foil For copper foil for laser processing with carrier foil, "carrier foil / peeling layer / electrolytic copper-tin alloy layer / copper foil" The layer structure is provided. Therefore, in order to measure the tin content of the electrolytic copper-tin alloy layer, it is preferable to employ the following method. In the case of the copper foil for laser processing with a carrier foil according to the present application, when the carrier foil is peeled off, the layer configuration is “peeling layer / electrolytic copper-tin alloy layer / copper foil”. And since the peeling layer at this time is comprised with the above-mentioned component, it does not affect the measurement of the tin content of the electrolytic copper-tin alloy layer. Therefore, the total copper content is measured using ICP analysis method, fluorescent X-ray apparatus, titration quantitative method, etc. for a solution in which the sample of layer structure of “peeling layer / electrolytic copper-tin alloy layer / copper foil” is completely dissolved. And "the amount of copper contained in the electrolytic copper-tin alloy layer" calculated by subtracting "the amount of copper converted from the cross-sectional thickness of the copper foil" from this total copper content and "the tin content in the solution" From this, the tin content (% by mass) can be calculated. In addition, if the thickness of the copper foil is known in advance by cross-sectional observation, etc., using a fluorescent X-ray film thickness measuring instrument, perform a composition analysis of the foil defined as a two-layer foil, and in the electrolytic copper-tin alloy layer The tin content (% by mass) can be calculated.
次に、本件発明に係る銅張積層体について説明する。本件発明に係る銅張積層体は、上記難溶性レーザー吸収層が前記赤外線レーザー光を照射される側に配置されるように、上記レーザー加工用銅箔と、絶縁層構成材料とが積層されたことを特徴とする。すなわち、本件発明に係る銅張積層体は、絶縁層構成材料と上記レーザー加工用銅箔とが積層されており、絶縁層構成材料/銅箔/難溶性レーザー吸収層(電解銅-スズ合金層)の順に積層された層構成を有する積層体であればどのようなものであってもよい。また、当該銅張積層体を得ることができれば、その製造方法に特に限定はない。例えば、いわゆるBステージの絶縁樹脂基材又は絶縁樹脂層に上記レーザー加工用銅箔又はキャリア箔付銅箔の銅箔側を積層し、加熱加圧することにより絶縁樹脂基材又は絶縁樹脂層上にレーザー加工用銅箔が積層された銅張積層体を得ることができる。なお、キャリア箔付レーザー加工用銅箔を用いた場合には、キャリア箔を適切な段階で除去すればよい。 3. Next, the copper clad laminate according to the present invention will be described. In the copper clad laminate according to the present invention, the copper foil for laser processing and the insulating layer constituting material are laminated so that the hardly soluble laser absorption layer is disposed on the side irradiated with the infrared laser light. It is characterized by that. That is, the copper-clad laminate according to the present invention is formed by laminating the insulating layer constituent material and the copper foil for laser processing, and the insulating layer constituent material / copper foil / slightly soluble laser absorbing layer (electrolytic copper-tin alloy layer). Any structure may be used as long as it has a layer structure stacked in the order of). Moreover, if the said copper clad laminated body can be obtained, there will be no limitation in particular in the manufacturing method. For example, the copper foil side of the copper foil for laser processing or the copper foil with carrier foil is laminated on the insulating resin base material or insulating resin layer of the so-called B stage, and heated and pressed on the insulating resin base material or insulating resin layer. A copper clad laminate in which a copper foil for laser processing is laminated can be obtained. When the copper foil for laser processing with carrier foil is used, the carrier foil may be removed at an appropriate stage.
次に、本件発明に係るプリント配線板の製造方法を説明する。ここでは、図2を参照しながら、本件発明に係るレーザー加工用銅箔10を用いて、MSAP法により配線パターンを形成する場合を例に挙げて説明する。なお、ここで用いるレーザー加工用銅箔10は、プライマー樹脂層11/銅箔(電解銅箔層)12/電解銅-スズ合金層13(難溶性レーザー吸収層)の層構成を備えるものとし、銅箔12の接着面には粗化処理層は設けられていないものとする。また、以下においては、配線層が絶縁層を介して3層以上積層した多層プリント配線板を製造する方法について説明する。但し、本件発明に係るプリント配線板の製造方法は多層プリント配線板の製造方法に限定されるものではなく、両面プリント配線板を製造する際にも適用可能である。 4). Next, a method for manufacturing a printed wiring board according to the present invention will be described. Here, a case where a wiring pattern is formed by the MSAP method using the
本実施例では、キャリア箔付レーザー加工用銅箔を、以下の工程A~工程Eにより作製した。 [Preparation of copper foil for laser processing with carrier foil]
In this example, a copper foil for laser processing with a carrier foil was produced by the following steps A to E.
CuSO4 ・5H2O:157g/l(Cu換算40g/l)
SnSO4 :127g/l(Sn換算70g/l)
C6H11O7Na:70g/l
フリーH2SO4:70g/l
液温:35℃
カソード電流密度:30A/dm2 (Copper-tin plating bath composition and electrolysis conditions)
CuSO 4 · 5H 2 O: 157g / l (Cu terms 40 g / l)
SnSO 4 : 127 g / l (Sn equivalent 70 g / l)
C 6 H 11 O 7 Na: 70 g / l
Free H 2 SO 4 : 70 g / l
Liquid temperature: 35 ° C
Cathode current density: 30 A / dm 2
CuSO4 ・5H2O:255g/l(Cu換算65g/l)
フリーH2SO4:150g/l
液温:45℃
カソード電流密度:15A/dm2 (Composition of copper plating bath and electrolysis conditions)
CuSO 4 · 5H 2 O: 255g / l (Cu terms 65 g / l)
Free H 2 SO 4 : 150 g / l
Liquid temperature: 45 ° C
Cathode current density: 15 A / dm 2
上述のキャリア箔付レーザー加工用銅箔を用いて、電解銅箔の接着面に、絶縁樹脂層構成材として厚み100μmのFR-4のプリプレグを熱間プレス加工により張り合わせた。そして、キャリア箔付レーザー加工用銅箔のキャリア箔を剥離層を介して引き剥がすことにより、キャリア箔を除去して銅張積層板を得た。 [Preparation of copper-clad laminate]
Using the above-mentioned copper foil for laser processing with carrier foil, a FR-4 prepreg having a thickness of 100 μm as an insulating resin layer constituting material was bonded to the adhesive surface of the electrolytic copper foil by hot pressing. And the carrier foil was removed by peeling off the carrier foil of the copper foil for laser processing with carrier foil through a peeling layer, and the copper clad laminated board was obtained.
比較例1では、電解銅-スズ合金層を備えていないこと以外は実施例と同様にしてピーラブルタイプのキャリア箔付電解銅箔を作製した。そして、このキャリア箔付電解銅箔を用いて、実施例と同様にして銅張積層板を作製した。 [Comparative Example 1]
In Comparative Example 1, a peelable type electrolytic copper foil with a carrier foil was produced in the same manner as in the Example except that the electrolytic copper-tin alloy layer was not provided. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
比較例2では、工程Cにおいて、下記組成の銅-スズめっき浴中で、キャリア箔を下記電解条件でカソード分極し、キャリア箔上に剥離層及び耐熱金属層を介して、厚み0.7μmの電解銅-スズ合金層を形成した以外は、実施例と同様にしてキャリア箔付電解銅箔を作製した。そして、このキャリア箔付電解銅箔を用いて、実施例と同様にして銅張積層板を作製した。 [Comparative Example 2]
In Comparative Example 2, in Step C, the carrier foil was cathodically polarized under the following electrolysis conditions in a copper-tin plating bath having the following composition, and the thickness of 0.7 μm was interposed on the carrier foil with a release layer and a heat-resistant metal layer. An electrolytic copper foil with a carrier foil was produced in the same manner as in Example except that the electrolytic copper-tin alloy layer was formed. And using this electrolytic copper foil with carrier foil, the copper clad laminated board was produced like the Example.
CuSO4 ・5H2O:79g/l(Cu換算20g/l)
SnSO4 :72g/l(Sn換算40g/l)
H2SO4:70g/l
液温:45℃
カソード電流密度:15A/dm2 (Copper-tin plating bath composition and electrolysis conditions)
CuSO 4 · 5H 2 O: 79g / l (Cu terms 20 g / l)
SnSO 4 : 72 g / l (Sn equivalent 40 g / l)
H 2 SO 4 : 70 g / l
Liquid temperature: 45 ° C
Cathode current density: 15 A / dm 2
比較例3では、比較例1のキャリア箔付電解銅箔を用いて、実施例と同様の方法で銅張積層板を作製した。そして、この銅張積層板の銅箔の表面に、市販の無電解スズめっき液を用いて、0.4μmの厚みの金属スズ層を形成した。そして、当該金属スズ層を形成した銅張積層板を200℃×30分の条件で加熱処理して、電解銅箔の銅成分と金属スズ層のスズ成分との間で相互拡散を起こさせ、当該銅箔の表層にスズ-銅を主体とする拡散合金層を備える銅張積層板を得た。 [Comparative Example 3]
In Comparative Example 3, using the electrolytic copper foil with carrier foil of Comparative Example 1, a copper clad laminate was produced in the same manner as in the example. Then, a metal tin layer having a thickness of 0.4 μm was formed on the surface of the copper foil of the copper clad laminate using a commercially available electroless tin plating solution. Then, the copper clad laminate on which the metal tin layer is formed is heat-treated at 200 ° C. for 30 minutes to cause mutual diffusion between the copper component of the electrolytic copper foil and the tin component of the metal tin layer, A copper-clad laminate having a diffusion alloy layer mainly composed of tin-copper on the surface layer of the copper foil was obtained.
1.評価方法
(1)レーザー孔開け加工性の評価
上記実施例及び比較例で作製した各銅張積層板を用いて、レーザー孔開け加工性能の評価には、炭酸ガスレーザーを用いた。このときの炭酸ガスレーザーによる孔開け加工条件は、加工エネルギー6.9mJ、パルス幅16μsec.、ビーム径120μmの条件で行った。 [Evaluation]
1. Evaluation Method (1) Evaluation of Laser Drilling Workability A carbon dioxide laser was used for evaluation of laser drilling performance using each copper-clad laminate produced in the above examples and comparative examples. The conditions for drilling with a carbon dioxide laser at this time were as follows: machining energy 6.9 mJ, pulse width 16 μsec. The beam diameter was 120 μm.
上記実施例及び比較例で作製した各銅張積層板を用いて、プリント配線板を製造過程で一般的に行われるデスミア工程及びマイクロエッチング工程と同様の処理を行い、各工程の前後における銅箔の厚みの変化を評価した。 (2) Evaluation of variation in thickness of copper foil Using each copper-clad laminate produced in the above examples and comparative examples, the same treatment as the desmear process and microetching process generally performed in the manufacturing process of printed wiring boards And the change in the thickness of the copper foil before and after each step was evaluated.
(1)レーザー孔開け加工性の評価
表1に、各銅張積層板に対して上記加工条件でビアホールを形成したときのトップ径を示す。ここで、トップ径とは、図2(b)に示すように、ビアホールの開口径をいう。表1に示すように、実施例と、比較例2及び比較例3で作製した銅張積層板では、スズを含有する電解銅-スズ合金層を最外層とし、この電解銅-スズ合金層にレーザー光を照射するため、黒化処理等のレーザー光の吸収率を高めるための前処理を施すことなく、レーザー加工により孔開けが可能であることが確認された。また、比較例1で作製した銅張積層板については、レーザー加工により直接孔開けすることができず、黒化処理等の何らかのレーザー光の吸収率を高めるための前処理を施さなければ、レーザー加工によりマイクロビアホールを形成することができないことが確認された。 2. Evaluation Results (1) Evaluation of Laser Drilling Workability Table 1 shows the top diameter when via holes are formed under the above processing conditions for each copper-clad laminate. Here, the top diameter refers to the opening diameter of the via hole as shown in FIG. As shown in Table 1, in the copper clad laminates produced in Examples and Comparative Examples 2 and 3, the electrolytic copper-tin alloy layer containing tin is the outermost layer, and this electrolytic copper-tin alloy layer In order to irradiate laser light, it was confirmed that drilling was possible by laser processing without performing pretreatment for increasing the absorption rate of laser light such as blackening treatment. In addition, the copper-clad laminate produced in Comparative Example 1 cannot be directly drilled by laser processing, and if no pretreatment for increasing the laser light absorption rate, such as blackening treatment, is performed, the laser It was confirmed that micro via holes cannot be formed by processing.
次に、図3に実施例と比較例1の銅張積層板の断面を示すFIB-SIM像を示す。図3に示すように、実施例で作製した銅張積層板は、2μmの厚みの電解銅箔層上に0.7μmの電解銅-スズ合金層を備えている。当該銅張積層板に対して、上述のとおり、デスミア工程を行った場合、電解銅-スズ合金層の表面は溶解し、電解銅-スズ合金層の厚みは0.21μm減少した。次に、当該銅張積層板に対して、上述のとおり、マイクロエッチング工程を施した場合、電解銅-スズ合金層の表面は溶解し、電解銅-スズ合金層の厚みは0.38μm減少した。このように、電解銅-スズ合金層はデスミア工程及びマイクロエッチング工程の際に溶解されるものの、当該電解銅-スズ合金層が存在することにより、銅箔の厚みには変化がなく、初期の厚み(2μm)を維持することができる。これに対して、比較例1で作製した銅張積層板は、電解銅箔層上に電解銅-スズ合金層を備えていないため、デスミア工程の際には0.10μm、マイクロエッチング工程の際に1.03μm厚みが減少する。また、実施例において、電解銅-スズ合金層中のスズ含有量は27.5質量%であり、図1に示したように、スズを含有しない電解銅箔と比較するとエッチング速度は遅い。このため、比較例1の銅張積層板では、実施例の銅張積層板と比較すると、エッチング量も大きくなり、銅箔の厚みにバラツキが生じる恐れが高くなる。 (2) Evaluation of Variation in Copper Foil Thickness Next, FIG. 3 shows FIB-SIM images showing cross sections of the copper clad laminates of Example and Comparative Example 1. As shown in FIG. 3, the copper clad laminate produced in the example is provided with a 0.7 μm electrolytic copper-tin alloy layer on a 2 μm thick electrolytic copper foil layer. As described above, when the desmear process was performed on the copper clad laminate, the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.21 μm. Next, when the copper-clad laminate was subjected to a microetching process as described above, the surface of the electrolytic copper-tin alloy layer was dissolved, and the thickness of the electrolytic copper-tin alloy layer was reduced by 0.38 μm. . Thus, although the electrolytic copper-tin alloy layer is dissolved in the desmear process and the microetching process, the presence of the electrolytic copper-tin alloy layer does not change the thickness of the copper foil, and the initial The thickness (2 μm) can be maintained. On the other hand, the copper clad laminate produced in Comparative Example 1 does not have an electrolytic copper-tin alloy layer on the electrolytic copper foil layer, so that it is 0.10 μm in the desmear process, and in the microetching process. The thickness is reduced to 1.03 μm. In the examples, the tin content in the electrolytic copper-tin alloy layer is 27.5% by mass, and as shown in FIG. 1, the etching rate is slower than that of the electrolytic copper foil not containing tin. For this reason, in the copper clad laminated board of the comparative example 1, compared with the copper clad laminated board of an Example, the amount of etchings also becomes large and there exists a possibility that variation may arise in the thickness of copper foil.
Claims (8)
- 銅エッチング液に対するエッチング性を有すると共に、そのエッチング速度が銅箔よりも遅く、且つ、赤外線レーザー光を吸収する難溶性レーザー吸収層を銅箔の表面に備えたことを特徴とするレーザー加工用銅箔。 Copper for laser processing characterized by having an etching property with respect to a copper etching solution, an etching rate slower than that of the copper foil, and a hardly soluble laser absorbing layer for absorbing infrared laser light on the surface of the copper foil. Foil.
- 前記難溶性レーザー吸収層は、スズ含有量が25質量%以上50質量%以下の電解めっき法により形成された電解銅-スズ合金層である請求項1に記載のレーザー加工用銅箔。 2. The copper foil for laser processing according to claim 1, wherein the hardly soluble laser absorption layer is an electrolytic copper-tin alloy layer formed by an electrolytic plating method having a tin content of 25% by mass or more and 50% by mass or less.
- 前記難溶性レーザー吸収層の厚みは、3μm以下である請求項1又は請求項2に記載のレーザー加工用電解銅合金箔。 The electrolytic copper alloy foil for laser processing according to claim 1 or 2, wherein the hardly soluble laser absorbing layer has a thickness of 3 µm or less.
- 前記銅箔の厚みは、7μm以下である請求項1~請求項3のいずれか一項に記載のレーザー加工用電解銅合金箔。 The electrolytic copper alloy foil for laser processing according to any one of claims 1 to 3, wherein the copper foil has a thickness of 7 µm or less.
- 前記銅箔の他方の表面には、粗化処理層及びプライマー樹脂層のうち少なくともいずれか一を備える請求項1~請求項4のいずれか一項に記載のレーザー加工用銅箔。 The copper foil for laser processing according to any one of claims 1 to 4, wherein at least one of a roughening treatment layer and a primer resin layer is provided on the other surface of the copper foil.
- 請求項1~請求項5のいずれか一項に記載のレーザー加工用銅箔の前記難溶性レーザー吸収層上にキャリア箔を剥離可能に備えたことを特徴とするキャリア箔付レーザー加工用銅箔。 6. A copper foil for laser processing with a carrier foil, wherein the copper foil for laser processing according to any one of claims 1 to 5 is provided with a peelable carrier foil on the hardly soluble laser absorbing layer. .
- 前記赤外線レーザー光が照射される側に前記難溶性レーザー吸収層が配置されるように、請求項1~請求項5のいずれか一項に記載のレーザー加工用銅箔と、絶縁層構成材料とが積層されたことを特徴とする銅張積層体。 The copper foil for laser processing according to any one of claims 1 to 5, an insulating layer constituting material, and the hardly soluble laser absorbing layer disposed on the side irradiated with the infrared laser light. A copper-clad laminate characterized in that is laminated.
- 銅エッチング液に対するエッチング性を有すると共に、そのエッチング速度が銅箔よりも遅く、且つ、赤外線レーザー光を吸収するレーザー吸収層を銅箔の表面に備えたレーザー加工用銅箔と、他の導体層とが絶縁層を介して積層された積層体に対して、赤外線レーザー光を難溶性レーザー吸収層に直接照射して層間接続用のビアホールを形成し、ビアホール内のスミアを除去するデスミア工程及び/又は無電解めっき工程の前処理としてのマイクロエッチング工程において、当該難溶性レーザー吸収層を当該銅箔の表面から除去すること、を特徴とするプリント配線板の製造方法。 A copper foil for laser processing having an etching property with respect to a copper etchant and having an etching rate slower than that of the copper foil and a laser absorbing layer for absorbing infrared laser light on the surface of the copper foil, and other conductor layers And a de-smear process for forming a via hole for interlayer connection by directly irradiating a hardly soluble laser absorption layer with an infrared laser beam to a laminate in which an insulating layer is laminated, and / or removing a smear in the via hole, and / or Alternatively, in the microetching process as a pretreatment of the electroless plating process, the hardly soluble laser absorbing layer is removed from the surface of the copper foil.
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JP2015504326A JP6304829B2 (en) | 2013-03-05 | 2014-03-04 | Copper foil for laser processing, copper foil for laser processing with carrier foil, copper-clad laminate, and method for producing printed wiring board |
KR1020157023938A KR102356407B1 (en) | 2013-03-05 | 2014-03-04 | Copper foil for laser processing, carrier-foil-supported copper foil for laser processing, copper-clad laminate, and process for producing printed wiring board |
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