WO2014054811A1 - 多層プリント配線基板の製造方法及びベース基材 - Google Patents
多層プリント配線基板の製造方法及びベース基材 Download PDFInfo
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- WO2014054811A1 WO2014054811A1 PCT/JP2013/077182 JP2013077182W WO2014054811A1 WO 2014054811 A1 WO2014054811 A1 WO 2014054811A1 JP 2013077182 W JP2013077182 W JP 2013077182W WO 2014054811 A1 WO2014054811 A1 WO 2014054811A1
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- printed wiring
- wiring board
- multilayer printed
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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
- H05K3/4682—Manufacture of core-less build-up multilayer circuits on a temporary carrier or on a metal foil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49822—Multilayer substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49894—Materials of the insulating layers or coatings
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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
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0061—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto a metallic substrate, e.g. a heat sink
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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
- H05K3/0097—Processing two or more printed circuits simultaneously, e.g. made from a common substrate, or temporarily stacked circuit boards
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- 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
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/0152—Temporary metallic carrier, e.g. for transferring material
Definitions
- the present invention relates to a method for manufacturing a multilayer printed wiring board and a base substrate.
- Patent Document 1 discloses a configuration in which a prepreg is employed as a copper foil carrier and the copper foil is laminated on the prepreg so as to be peeled off.
- a multilayer printed wiring board usually includes a configuration in which a build-up layer including one or more wiring layers and one or more insulating layers is laminated on a resin base substrate.
- the wiring board may be bent and deformed during the manufacturing process, or may be warped, thereby hindering the mounting process.
- an object of the present invention is to provide a base substrate that functions as a support when a thin multilayer printed wiring board having a configuration different from the conventional one is manufactured.
- the method for producing a multilayer printed wiring board according to the present invention includes a first step of preparing a base substrate in which a resin layer is laminated via a release agent layer on at least one main surface of a metal plate carrier; And a second step of laminating one or more buildup layers on the resin layer of the base substrate.
- the substrate thickness of the plate carrier is preferably 5 ⁇ m or more and 1600 ⁇ m or less.
- the peel strength between the plate carrier and the resin layer is preferably 10 gf / cm or more and 200 gf / cm or less.
- the peel strength between the plate-like carrier and the resin layer after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is preferably 10 gf / cm or more and 200 gf / cm or less.
- the method further includes a third step of separating the resin layer on which the buildup layer is laminated and the plate carrier.
- the method further includes a fourth step of laminating a second resin layer different from the first resin layer and a further build-up layer on the multilayer printed wiring board obtained in the third step.
- the resin layer is preferably a prepreg.
- the resin layer preferably has a glass transition temperature Tg of 120 to 320 ° C.
- the build-up layer preferably includes one or more insulating layers and one or more wiring layers.
- the one or more wiring layers included in the build-up layer may be a patterned or non-patterned metal foil.
- the one or more insulating layers included in the buildup layer may be a prepreg.
- the build-up layer preferably includes a single-sided or double-sided metal-clad laminate.
- the build-up layer may be formed using at least one of a subtractive method, a full additive method, or a semi-additive method.
- the method further includes a fifth step of performing a dicing process on the laminate in which the buildup layer is laminated on the base substrate.
- one or more grooves are formed in the laminate in which the buildup layer is laminated on the base substrate by the dicing process, and the buildup layer can be separated into pieces by the grooves.
- the method further includes a sixth step of forming via wiring for one or more insulating layers included in the buildup layer.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
- the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product may be used alone or in combination.
- the release agent layer is preferably made of a compound having 2 or less mercapto groups in the molecule.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr) It is preferable to use the aluminate compound, titanate compound, zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products, which are used alone or in combination.
- the release agent layer may be a resin coating film composed of silicone and any one or a plurality of resins selected from epoxy resins, melamine resins, and fluororesins.
- the plate carrier is preferably made of copper or a copper alloy.
- the wiring layer is preferably made of copper or a copper alloy.
- the multilayer printed wiring board according to the present invention is a multilayer printed wiring board manufactured by the method for manufacturing a multilayer printed wiring board described above.
- a base substrate according to the present invention is a base substrate used in a method for manufacturing a multilayer printed wiring board, and is a metal plate carrier and a separation formed on at least one main surface of the plate carrier.
- a mold agent layer and a resin layer laminated on the plate-like carrier via the release agent layer are provided, and the resin layer and the plate-like carrier are peelable.
- the substrate thickness of the plate carrier is preferably 5 ⁇ m or more and 1600 ⁇ m or less.
- the peel strength between the plate carrier and the resin layer is preferably 10 gf / cm or more and 200 gf / cm or less.
- the peel strength between the plate-like carrier and the resin layer after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is preferably 10 gf / cm or more and 200 gf / cm or less.
- the plate carrier is preferably made of copper or a copper alloy.
- the resin layer is preferably made of prepreg.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
- the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product may be used alone or in combination.
- the release agent layer is preferably made of a compound having 2 or less mercapto groups in the molecule.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr) It is preferable to use the aluminate compound, titanate compound, zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products, which are used alone or in combination.
- the release agent layer may be a resin coating film composed of silicone and any one or a plurality of resins selected from epoxy resins, melamine resins, and fluororesins.
- the laminate according to the present invention is a laminate in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.) Or a hydrolyzate thereof, or a condensate of the hydrolyzate, alone or in combination.
- the laminate according to the present invention is a laminate in which a release agent layer is laminated on at least one main surface of a metal plate carrier, and the release agent layer has two or less release agents in the molecule.
- a compound having a mercapto group is used.
- the laminate according to the present invention is a laminate in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
- the aluminate compound, the titanate compound, the zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products are used singly or in combination.
- the release agent layer is a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin.
- the plate carrier is made of copper or a copper alloy.
- the metal plate carrier and the buildup layer can be separated, and a thin multilayer printed wiring board can be efficiently manufactured.
- FIG. 1 is a schematic cross-sectional view of a base substrate according to a first embodiment of the present invention. It is a schematic process drawing which shows the state which laminated
- FIG. 1 is a schematic cross-sectional view of a base substrate.
- FIG. 2 is a schematic process diagram showing a state in which a buildup layer is laminated on a base substrate.
- FIG. 3 is a process diagram schematically showing a process of peeling the multilayer printed wiring board and the plate-like carrier.
- the base substrate 100 includes a metal plate carrier 10 having a predetermined thickness, a release agent layer 20 laminated on the upper surface (main surface) of the plate carrier 10, and a release agent layer 20.
- the prepreg 30 which is an example of the resin layer laminated
- the release agent layer 20 is not necessarily formed on the entire upper surface of the plate-like carrier 10, and similarly, the prepreg 30 is not necessarily stacked on the entire upper surface of the release agent layer 20.
- the shape of the plate-like carrier 10 and the prepreg 30 as viewed from above is not limited to a rectangle, and may be another shape such as a circle.
- the prepreg 30 is typically a layer that should constitute the lowermost layer of the multilayer printed wiring board. In other words, the prepreg 30 is equal to the insulating layer 40 constituting the buildup layer 110. This point is also apparent from the following description.
- the order of stacking the constituent layers of the base substrate 100 is arbitrary, for example, after preparing the plate carrier 10 first, the release agent layer 20 is stacked on the upper surface (main surface) of the plate carrier 10, Next, the prepreg 30 may be laminated via the release agent layer 20. Alternatively, the release agent layer 20 may be laminated on the lower surface (main surface) of the prepreg 30, and the laminate of the prepreg 30 and the release agent layer 20 may be laminated on the plate carrier 10.
- the release agent layer 20 can be formed on the prepreg 30 or the plate-like carrier 10 by utilizing a normal coating technique. The thickness of the plate carrier 10 or the prepreg 30 can be adjusted by any known means and method.
- a buildup layer 110 including one or more insulating layers 40 and one or more wiring layers 50 is laminated on the prepreg 30 of the base substrate 100.
- the buildup layer 110 is a laminate of one insulating layer 40 and one wiring layer 50.
- the buildup layer 110 having a two-layer structure including the prepreg 30 is illustrated.
- the insulating layer 40 of the buildup layer 110 is preferably made of a resin layer, more preferably a prepreg containing a thermosetting resin.
- the wiring layer 50 of the buildup layer 110 is preferably a patterned or unpatterned metal layer, preferably a metal foil or a plated metal layer.
- the buildup layer 110 is formed by repeatedly laminating the insulating layer 40 and the wiring layer 50 in order. After the buildup layer 110 is laminated on the base substrate 100, the buildup layer 110 is separated from the base substrate 100, whereby the buildup layer 110 can be suitably obtained as a thin multilayer printed wiring board.
- the base substrate 100 used for stacking the buildup layer 110 is not included.
- the multilayer printed wiring board according to the present embodiment has a “thin” configuration.
- “Thin” means, for example, that the thickness of the multilayer printed wiring board is 400 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
- the multilayer printed wiring board The thickness may exceed 400 ⁇ m.
- the base substrate 100 itself is also heated or physically or chemically treated, and in some cases, immersed in a chemical solution. Even after such a process, the peelability between the multilayer printed wiring board schematically shown in FIG. 3, that is, the lowermost prepreg 30 of the multilayer printed wiring board and the plate-like carrier 10 is ensured.
- the release agent layer 20 remains on the plate carrier 10 side, but this is not necessarily the case.
- the constituent materials and layer thicknesses of the insulating layer 40 and the wiring layer 50 are arbitrary, and one wiring layer 50 may be composed of a stack of one or more conductive layers, and one insulating layer 40 may have one or more insulating layers. You may comprise from lamination
- the wiring layer 50 is composed of, for example, one or more metal foils.
- the insulating layer 40 is composed of one or more resin layers, and is preferably a thermosetting resin layer.
- the wiring layer 50 does not necessarily have to be patterned and does not necessarily have to be electrically connected to other wiring layers. Providing the floating wiring layer 50 may be effective when controlling the capacitance generated between the wiring layers or adjusting the mechanical strength of the multilayer printed wiring board.
- the buildup layer 110 includes one or more insulating layers 40 and one or more wiring layers 50.
- one or more wiring layers 50 included in the buildup layer 110 are patterned or unpatterned metal foil.
- one or more insulating layers 40 included in the buildup layer 110 are prepregs.
- the build-up layer 110 includes a single-sided or double-sided metal-clad laminate.
- the plate-like carrier 10 is a flat plate made of metal, preferably copper or copper alloy, and may have some flexibility depending on its size, but can ensure the function as a support substrate. It is desirable to have a certain degree of rigidity.
- the plate-like carrier 10 is typically made of a metal foil having a thickness of 5 ⁇ m or more, more preferably 10 ⁇ m or more, 30 ⁇ m or more, 35 ⁇ m or more, 50 ⁇ m or more, 65 ⁇ m or more, 70 ⁇ m or more, 80 ⁇ m or more, 100 ⁇ m or more. Can do.
- the plate-like carrier 10 is typically a metal foil having a thickness of 1600 ⁇ m or less, more preferably 1500 ⁇ m or less, 1350 ⁇ m or less, 1000 ⁇ m or less, 800 ⁇ m or less, 500 ⁇ m or less, 400 ⁇ m or less, 300 ⁇ m or less, or 105 ⁇ m or less. Can do. Moreover, the plate-shaped carrier 10 can use copper foil or copper alloy foil suitably.
- the plate-like carrier 10 may be a flat plate produced by rolling a copper material, or may be a flat plate formed by laminating copper materials in multiple layers. In this case, the flat plate is 1600 ⁇ m or more. It may have a thickness.
- a copper material such as a copper foil obtained by electrolysis may be used for the plate-like carrier 10.
- a copper alloy may be used as a constituent material of the plate-like carrier 10. By utilizing the copper alloy, the hardness of the plate-like carrier 10 can be increased.
- the copper alloy includes at least one element selected from the group consisting of Ni, Si, Zn, Sn, Ti, P, Cr, B, Ag, Mg, Fe, V, Au, Pd, Co, Mn, beryllium and cadmium.
- a copper alloy to which 0 to 80% by mass in total is added can be exemplified.
- the material of the plate-like carrier 10 is not particularly limited as long as it is a metal, and examples thereof include copper, gold, silver, iron, nickel, aluminum, chromium, titanium, zinc, and magnesium. Alloys using these, such as copper alloys and iron alloys, may also be used.
- Typical examples of copper include copper having a purity of 99.90% by mass or more, such as phosphorus deoxidized copper, oxygen-free copper, and tough pitch copper as defined in JIS H0500. Copper or copper alloy containing 0.001 to 4.0% by mass in total of one or more of Sn, Ag, Au, Co, Cr, Fe, In, Ni, P, Si, Te, Ti, Zn and Zr It can also be.
- Examples of the copper alloy further include titanium copper, phosphor bronze, Corson alloy, red brass, brass, and white.
- Titanium copper typically contains 0.5% to 5.0% by mass of Ti, with the balance being composed of copper and inevitable impurities. Titanium copper further contains one or more of Fe, Co, V, Nb, Mo, B, Ni, P, Zr, Mn, Zn, Si, Mg, and Cr in total of 2.0% by mass or less. Also good.
- Phosphor bronze typically refers to a copper alloy containing copper as a main component and containing Sn and a lower mass of P.
- phosphor bronze contains 3.5 to 11% by mass of Sn and 0.03 to 0.35% by mass of P, and has a composition consisting of the balance copper and inevitable impurities.
- Phosphor bronze may contain 1.0% by mass or less of elements such as Ni and Zn in total.
- Corson alloy typically refers to a copper alloy in which an element that forms a compound with Si (for example, any one or more of Ni, Co, and Cr) is added and precipitates as second-phase particles in the parent phase.
- the Corson alloy contains 1.0 to 4.0% by mass of Ni and 0.2 to 1.3% by mass of Si, and has a composition composed of the remaining copper and inevitable impurities.
- the Corson alloy contains 1.0 to 4.0% by mass of Ni, 0.2 to 1.3% by mass of Si, 0.03 to 0.5% by mass of Cr, the remaining copper and unavoidable The composition is composed of mechanical impurities.
- the Corson alloy contains 1.0 to 4.0 mass% Ni, 0.2 to 1.3 mass% Si, 0.5 to 2.5 mass% Co, the balance copper and It has a composition composed of inevitable impurities.
- the Corson alloy has a Ni content of 1.0 to 4.0 mass%, a Si content of 0.2 to 1.3 mass%, a Co content of 0.5 to 2.5 mass%, and a Cr content of 0.03. It is contained at 0.5% by mass and has a composition composed of the balance copper and inevitable impurities.
- the Corson alloy contains 0.2 to 1.3% by mass of Si and 0.5 to 2.5% by mass of Co, and has a composition composed of the balance copper and inevitable impurities.
- the Corson alloy may be added to the Corson alloy.
- these other elements are generally added up to about 2.0 mass% in total.
- the Corson alloy has a Ni content of 1.0 to 4.0 mass%, a Si content of 0.2 to 1.3 mass%, a Sn content of 0.01 to 2.0 mass%, and a Zn content of 0. 0.01 to 2.0% by mass, and the composition is composed of the balance copper and unavoidable impurities.
- Brass is an alloy of copper and zinc, particularly a copper alloy containing 20% by mass or more of zinc.
- the upper limit of zinc is not particularly limited, but is 60% by mass or less, preferably 45% by mass or less, or 40% by mass or less.
- the red copper is an alloy of copper and zinc and means a copper alloy containing 1 to 20% by mass of zinc, more preferably 1 to 10% by mass of zinc. Further, the red lead may contain 0.1 to 1.0% by mass of tin.
- Western white is a copper alloy containing copper as a main component, copper from 60% by mass to 75% by mass, nickel from 8.5% by mass to 19.5% by mass, and zinc from 10% by mass to 30% by mass.
- aluminum and aluminum alloy for example, aluminum containing 99% by mass or more can be used. Specifically, Al: 99.00 mass% aluminum represented by alloy numbers 1085, 1080, 1070, 1050, 1100, 1200, 1N00, and 1N30 described in JIS H 4000 or an alloy thereof is used. Can do.
- nickel and nickel alloy for example, nickel containing 99% by mass or more can be used. Specifically, nickel of 99.0% by mass or more represented by alloy numbers NW2200 and NW2201 described in JIS H4551 or an alloy thereof can be used.
- iron alloy for example, stainless steel, mild steel, iron-nickel alloy or the like can be used.
- SUS301, SUS304, SUS310, SUS316, SUS430, SUS631 (all are JIS standards) etc. can be used for stainless steel.
- the mild steel a mild steel having 0.15% by mass or less of carbon can be used, and a mild steel described in JIS G3141 can be used.
- the iron-nickel alloy contains 35 to 85% by mass of Ni and the balance is made of Fe and inevitable impurities.
- an iron-nickel alloy described in JIS C2531 can be used.
- well-known metals such as aluminum, aluminum alloy, nickel, a nickel alloy, iron, an iron alloy, and stainless steel, can also be used for a plate-shaped carrier.
- the Vickers hardness (HV) of the plate carrier 10 is typically 30 to 100 (F / N) / (d / mm) 2 , preferably 50 to 80 (F / N) / (d / mm) 2 . It is desirable to ensure sufficient hardness of a flat plate made of copper or copper alloy as the plate-like carrier 10.
- the plate carrier 10 may be subjected to a surface treatment.
- a surface treatment For example, metal plating for the purpose of imparting heat resistance (Ni plating, Ni—Zn alloy plating, Cu—Ni alloy plating, Cu—Zn alloy plating, Zn plating, Cu—Ni—Zn alloy plating, Co—Ni alloy plating, etc. ), Chromate treatment (including the case where one or more alloy elements such as Zn, P, Ni, Mo, Zr, Ti, etc.
- the chromate treatment liquid for imparting rust prevention and discoloration resistance, surface roughness (For example, copper electrodeposition grains, Cu—Ni—Co alloy plating, Cu—Ni—P alloy plating, Cu—Co alloy plating, Cu—Ni alloy plating, Cu—Co alloy plating, And copper alloy plating such as Cu—As alloy plating and Cu—As—W alloy plating).
- the roughening treatment affects the peel strength between the plate-like carrier 10 and the release agent layer 20, and the chromate treatment also has a great influence.
- Chromate treatment is important from the viewpoint of rust prevention and discoloration resistance, but since it tends to significantly increase the peel strength, it is also meaningful as a means for adjusting the peel strength.
- a nickel-zinc (Ni-Zn) alloy plating treatment and a chromate (Cr-Zn chromate) treatment may be performed on the glossy surface of a copper material under the following conditions.
- Nickel-zinc alloy plating Ni concentration 17g / L (added as NiSO 4 ) Zn concentration 4g / L (added as ZnSO 4 ) pH 3.1 Liquid temperature 40 °C Current density 0.1-10A / dm 2 Plating time 0.1 to 10 seconds
- the release agent layer 20 may be selected from any material that is relatively strongly fixed to the plate carrier 10 and relatively weakly fixed to the prepreg 30. As described above, the base substrate 100 may be heated and chemically or physically processed in the build-up layer 110 stacking process. From this point of view, it is desirable that the release agent layer 20 also has heat resistance and chemical resistance and is not easily altered or eroded by chemicals.
- the release agent layer 20 can be formed on the plate-like carrier 10 by any method such as spin coating, dip coating, spray coating, and printing, but is not particularly limited thereto.
- the upper surface of the plate-like carrier 10 on which the release agent layer 20 is formed may be either a rough surface (M surface) or a glossy surface (S surface), but is preferably a glossy surface rather than a rough surface. If a rolled metal foil, more preferably a rolled copper foil, is used as the plate-like carrier, both sides become glossy surfaces, and therefore it is more desirable when the release agent layer 20 is formed on both sides of the plate-like carrier. Thereby, the variation of the roughness of the upper surface of the plate-like carrier 10 on which the release agent layer 20 is laminated can be suppressed, and the quality of the base substrate 100 can be stabilized.
- the layer thickness of the release agent layer 20 is typically 0.001 to 10 ⁇ m, preferably 0.001 to 0.1 ⁇ m.
- Silane Compound The constituent material of the release agent layer 20 should not be limited to those disclosed in the present application or available at the present time.
- a silane compound represented by the following chemical formula and its hydrolysis product It is preferable to use a single product or a combination of multiple hydrolysis products in the release agent layer 20.
- R 1 is an alkoxy group or a halogen atom
- R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
- Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.
- the silane compound must have at least one alkoxy group.
- a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom
- a substituent is comprised only by group, there exists a tendency for the adhesiveness of the mold release agent layer 20 and the plate-shaped carrier 10 surface to fall too much.
- the silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have at least one. This is because when the hydrocarbon group does not exist, the adhesion between the release agent layer 20 and the surface of the plate-like carrier 10 tends to increase.
- the alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.
- the silane compound has three alkoxy groups and the hydrocarbon group ( It preferably has one (including a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom).
- R 3 and R 4 are alkoxy groups.
- Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group and the like, straight chain, branched or cyclic carbon number of 1-20, preferably carbon number of 1-10, more preferably carbon number of 1- 5 alkoxy groups.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- alkyl group examples include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, and n-hexyl.
- cycloalkyl group examples include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, which have 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms.
- An alkyl group is mentioned.
- the aryl group includes a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, etc., having 6 to 20, preferably 6 to 14 carbon atoms.
- an alkyl group eg, tolyl group,
- one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.
- Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo-pentyl.
- propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of availability.
- a compound having two or less mercapto groups in the molecule may be used for the release agent layer 20.
- examples thereof include thiol, dithiol, thiocarboxylic acid or a salt thereof, dithiocarboxylic acid or a salt thereof, thiosulfonic acid or a salt thereof, and dithiosulfonic acid or a salt thereof, and at least one selected from these is used. be able to.
- Thiol has one mercapto group in the molecule and is represented by, for example, R-SH.
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- Dithiol has two mercapto groups in the molecule and is represented by, for example, R (SH) 2 .
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- Two mercapto groups may be bonded to the same carbon, or may be bonded to different carbons or nitrogens.
- the thiocarboxylic acid is one in which a hydroxyl group of an organic carboxylic acid is substituted with a mercapto group, and is represented by, for example, R—CO—SH.
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- the thiocarboxylic acid can also be used in the form of a salt. A compound having two thiocarboxylic acid groups can also be used.
- Dithiocarboxylic acid is one in which two oxygen atoms in the carboxy group of an organic carboxylic acid are substituted with sulfur atoms, and is represented by, for example, R- (CS) -SH.
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- Dithiocarboxylic acid can also be used in the form of a salt.
- a compound having two dithiocarboxylic acid groups can also be used.
- the thiosulfonic acid is obtained by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, and is represented by, for example, R (SO 2 ) -SH.
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- thiosulfonic acid can be used in the form of a salt.
- Dithiosulfonic acid is one in which two hydroxyl groups of organic disulfonic acid are substituted with mercapto groups, and is represented by, for example, R-((SO 2 ) -SH) 2 .
- R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
- Two thiosulfonic acid groups may be bonded to the same carbon, or may be bonded to different carbons.
- Dithiosulfonic acid can also be used in the form of a salt.
- examples of the aliphatic hydrocarbon group suitable as R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.
- alkyl group examples include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n And straight-chain or branched alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as -hexyl group, n-octyl group, and n-decyl group. .
- cycloalkyl group is not limited, but it has 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., preferably 5 to 7 carbon atoms.
- cycloalkyl group preferably 3 to 10 carbon atoms.
- suitable aromatic hydrocarbon groups as R include phenyl groups, phenyl groups substituted with alkyl groups (eg, tolyl groups, xylyl groups), 1- or 2-naphthyl groups, anthryl groups, and the like. -20, preferably 6-14 aryl groups, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.
- heterocyclic group suitable as R examples include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, which may contain either or both of a hydroxyl group and an amino group.
- Preferred examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2, propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1-hexanol, 1- Octanethiol, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol, thiobenzoic acid, Examples include 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, and 2-mercapto-benzothiazole. Of these, 3-mercapto-1,2-propanediol is preferred from the viewpoint of water solubility and waste disposal.
- Metal alkoxide An aluminate compound, titanate compound, zirconate compound having a structure represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a metal alkoxide) alone Or by mixing and using the plate-like carrier 10 and the prepreg 30 together, the adhesion is moderately lowered, and the peel strength can be adjusted to a range as described later.
- R 1 is an alkoxy group or a halogen atom
- R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms. Any one of these substituted hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, m is an integer from 1 to M, and R At least one of 1 is an alkoxy group.
- M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.
- the metal alkoxide must have at least one alkoxy group.
- a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom
- a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much.
- the metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have 0-2. This is because when three or more hydrocarbon groups are present, the adhesion between the plate-like carrier and the metal foil surface tends to be excessively lowered.
- the alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.
- the metal alkoxide has two or more alkoxy groups and the hydrocarbon group (one It preferably has one or two (including a hydrocarbon group in which the above hydrogen atom is substituted with a halogen atom).
- alkyl group examples include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n And straight-chain or branched alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as -hexyl group, n-octyl group, and n-decyl group. .
- cycloalkyl group is not limited, but it has 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., preferably 5 to 7 carbon atoms.
- cycloalkyl group preferably 3 to 10 carbon atoms.
- examples of the aromatic hydrocarbon group suitable as R 2 include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples thereof include 6 to 20, preferably 6 to 14, aryl groups, and these hydrocarbon groups may contain one or both of a hydroxyl group and an amino group.
- one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.
- aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or iso-propyldimethoxyaluminum, n-, iso- or tert-butyldimethoxyaluminum, n-, iso- or neo- Pentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; alkyl-substituted phenyl dimethoxy aluminum (for example, p- (methyl) phenyl dimethoxy aluminum), dimethylmethoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethyl Aluminum, n-, iso- or tert-butyldieth
- titanate compounds examples include tetramethoxy titanium, methyl trimethoxy titanium, ethyl trimethoxy titanium, n- or iso-propyl trimethoxy titanium, n-, iso- or tert-butyl trimethoxy titanium, n-, iso- Or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (eg p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxy Titanium, tetraethoxy titanium, methyl triethoxy titanium, ethyl triethoxy titanium, n- or iso-propyl triethoxy titanium, n-, iso
- zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium, n-, iso- Or neo-pentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl-substituted phenyltrimethoxyzirconium (eg, p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxy Zirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltrie
- the base substrate 100 can be manufactured by bringing the plate carrier 10 and the prepreg 30 into close contact with each other by hot pressing. For example, after applying the metal alkoxide in the molecule to the bonding surface of the plate-like carrier 10 and / or the prepreg 30, the B-stage resin prepreg 30 is hot-press laminated on the plate-like carrier 10. Can be manufactured.
- Metal alkoxide can be used in the form of an aqueous solution.
- Alcohols such as methanol and ethanol can be added in order to increase the solubility in water.
- the addition of alcohol is particularly effective when a highly hydrophobic metal alkoxide is used.
- the concentration of the metal alkoxide in the aqueous solution can be 0.001 to 1.0 mol / L, and typically 0.005 to 0.2 mol / L.
- the pH of the aqueous solution of metal alkoxide is not particularly limited and can be used on either the acidic side or the alkaline side.
- it can be used at a pH in the range of 3.0 to 10.0.
- the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .
- the adjustment of the peel strength for realizing such adhesion is composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin. This is done by using a resin coating. Such a resin coating film is baked under predetermined conditions as described later, and is hot-pressed and bonded between the plate-like carrier and the metal foil, so that the adhesiveness is appropriately lowered and peeled. This is because the strength can be adjusted to a range described later.
- Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, Examples thereof include brominated phenoxy resin.
- the melamine-based resin examples include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol-modified melamine resin.
- the melamine resin may be a mixed resin of the resin and a butylated urea resin, a butylated benzoguanamine resin, or the like.
- the number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000.
- the resin can be made into a paint and the adhesive strength of the resin coating film can be easily adjusted to a predetermined range.
- examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.
- silicone examples include methylphenyl polysiloxane, methyl hydropolysiloxane, dimethyl polysiloxane, modified dimethyl polysiloxane, and mixtures thereof.
- the modification is, for example, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification.
- the resin coating film if the film thickness is too small, the resin coating film is too thin and difficult to form, so that the productivity is likely to decrease. Moreover, even if a film thickness exceeds a fixed magnitude
- the resin coating film silicone functions as a release agent for the resin coating film. Therefore, if the total amount of epoxy resin and melamine resin is too much compared to silicone, a resin coating film is applied between the plate carrier 10 and the prepreg 30 (or the buildup layer 110 including the prepreg 30). Since the peel strength is increased, the peelability of the resin coating film is lowered, and it may not be easily peeled manually. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-described peeling strength is reduced, and thus the peeling may occur at the time of transportation or processing. From this viewpoint, the total of the epoxy resin and the melamine resin is preferably included in an amount of 10 to 1500 parts by weight, more preferably 20 to 800 parts by weight with respect to 100 parts by weight of silicone. Is preferred.
- Fluorine resin also functions as a mold release agent, like silicone, and has the effect of improving the heat resistance of the resin coating film. If the fluororesin is too much compared to silicone, the above-mentioned peel strength becomes small, so that it may be peeled off during transport or processing, and the temperature required for the baking process described later increases, which is uneconomical. From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of silicone.
- the resin coating film is selected from SiO 2 , MgO, Al 2 O 3 , BaSO 4, and Mg (OH) 2 in addition to silicone, epoxy resin and / or melamine resin, and, if necessary, fluororesin 1 You may further contain the surface roughening particle
- the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the plate-like carrier or metal foil to which the resin coating film is applied becomes uneven and becomes a matte surface.
- the content of the surface roughening particles is not particularly limited as long as the resin coating is roughened, but it is preferably 1 to 10 parts by mass with respect to 100 parts by mass of silicone.
- the particle diameter of the surface roughened particles is preferably 15 nm to 4 ⁇ m.
- the particle diameter means an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph or the like.
- SEM scanning electron microscope
- the amount of irregularities on the surface of the plate-like carrier or metal foil is about 4.0 ⁇ m in terms of the maximum height roughness Ry defined by JIS.
- the base substrate 100 includes a step of applying the above-described resin coating on the surface of a coating object (at least one of the plate carrier 10 and the prepreg 30) and a baking step of curing the applied resin coating. Obtained through the procedure. Hereinafter, each step will be described.
- the coating process consists of coating the object to be coated (at least one of the plate-like carrier 10 and the prepreg 30), silicone as the main agent, epoxy-based resin as the curing agent, melamine-based resin, and fluorine as a release agent as necessary.
- This is a step of forming a resin coating film by applying a resin coating composed of a resin.
- the resin paint is obtained by dissolving an epoxy resin, a melamine resin, a fluororesin, and silicone in an organic solvent such as alcohol.
- the blending amount (addition amount) in the resin coating is preferably 10 to 1500 parts by mass of the total of the epoxy resin and the melamine resin with respect to 100 parts by mass of the silicone.
- the fluororesin is preferably 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
- the coating method in the coating process is not particularly limited as long as a resin coating film can be formed, but a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, a method using an electrostatic coating machine, etc. are used. In view of the uniformity of the resin coating film and the ease of work, the gravure coating method is preferred.
- the coating amount is preferably 1.0 to 2.0 g / m 2 so that the resin coating film 3 has a preferable film thickness: 0.5 to 5 ⁇ m.
- the gravure coating method is a method in which a resin coating film is formed on the surface of a coating object by transferring the resin paint filled in the recesses (cells) provided on the roll surface to the coating object. Specifically, the lower part of the lower roll having cells provided on the surface is immersed in the resin paint, and the resin paint is pumped into the cell by the rotation of the lower roll. Then, the coating object is disposed between the lower roll and the upper roll disposed on the upper side of the lower roll, and the lower roll and the upper roll are pressed while pressing the coating object against the lower roll with the upper roll. By rotating, the coating object is conveyed and the resin paint pumped into the cell is transferred (applied) to one side of the coating object.
- a doctor blade on the incoming side of the coating object so as to come into contact with the surface of the lower roll, excess resin paint pumped to the roll surface other than the cell is removed, and the surface of the coating object is removed. A predetermined amount of resin paint is applied to the substrate.
- a smoothing roll may be arranged on the carry-out side of the coating object to maintain the smoothness of the resin coating film.
- the baking step is a step of subjecting the resin coating film formed in the coating step to a baking treatment at 125 to 320 ° C. (baking temperature) for 0.5 to 60 seconds (baking time).
- a baking temperature is the temperature reached by the prepreg 30.
- a conventionally well-known apparatus is used as a heating means used for a baking process.
- the baking is insufficient, for example, when the baking temperature is less than 125 ° C. or when the baking time is less than 0.5 seconds, the resin coating becomes insufficiently cured, and the peel strength exceeds 200 gf / cm, The peelability is reduced.
- baking is an excessive condition, for example, when baking temperature exceeds 320 degreeC, a resin coating film deteriorates, the said peeling strength exceeds 200 gf / cm, and the workability
- a plate-shaped carrier may change in quality by high temperature. Further, when the baking time exceeds 60 seconds, the productivity is deteriorated.
- the resin coating in the application step includes silicone as a main agent, epoxy resin as a curing agent, melamine resin, fluororesin as a release agent, SiO 2 , MgO, al 2 O 3, BaSO 4 and Mg (OH) may be made of one or more surface roughening particles selected from 2.
- the resin paint is obtained by further adding surface roughening particles to the above-described silicone-added resin solution.
- the surface of the resin coating film becomes uneven, and the unevenness causes the plate-like carrier 10 to become uneven, resulting in a matte surface.
- the compounding amount (addition amount) of the surface roughening particles in the resin coating is 1 to 10 parts by mass with respect to 100 parts by mass of silicone.
- the surface roughened particles have a particle size of 15 nm to 4 ⁇ m.
- the production method according to the present invention is as described above. However, in carrying out the present invention, other steps may be included between or before and after each step within a range that does not adversely affect each step. . For example, you may perform the washing
- the prepreg 30 is an example of a resin layer that forms a base layer of a multilayer printed wiring board.
- the prepreg 30 is a composite of an arbitrary base material and an arbitrary filling material.
- the filling material is made from a liquid in a state where the base material such as a nonwoven fabric or a woven fabric is impregnated with the filling material such as a synthetic resin. Obtained by solidification.
- the prepreg 30 has a high insulating property and a desired mechanical strength.
- the resin that is a constituent material of the prepreg 30 is illustratively a phenol resin, a polyimide resin, an epoxy resin, natural rubber, pine resin, or the like, but is not limited thereto.
- the prepreg 30 before mounting on the plate-like carrier 10 is preferably in a B-stage state, and thereby sufficient strength can be ensured.
- the prepreg 30 desirably has a high glass transition temperature Tg.
- the glass transition temperature Tg of the prepreg 30 is, for example, 120 to 320 ° C., preferably 170 to 240 ° C.
- the glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).
- the prepreg 30 is laminated and fixed on the upper surface of the plate-like carrier 10 on which the release agent layer 20 is formed by thermocompression bonding by hot pressing or the like.
- hot pressing conditions it is preferable to perform hot pressing at a pressure of 30 to 40 kg / cm 2 and a temperature higher than the glass transition temperature of the prepreg 30.
- the surface temperature of the press member in contact with the prepreg 30 when the prepreg 30 is laminated and fixed is preferably 140 to 320 ° C.
- the thickness of the prepreg 30 is not particularly limited, and is set to a thickness that has flexibility or a thickness that does not have flexibility. However, since it is desirable for the prepreg 30 to have mechanical strength and rigidity when the buildup layer 110 is laminated, it is not appropriate to make it extremely thin. In addition, if the prepreg 30 is extremely thick, heat propagation through the prepreg 30 is difficult to occur, and thus a non-uniform heat distribution occurs in the plane of the prepreg 30 during hot pressing, making it difficult to achieve sufficient hot pressing. There is a fear. In view of this point, the thickness of the prepreg 30 is set to 50 to 900 ⁇ m, more preferably 100 to 400 ⁇ m.
- the prepreg 30 is sufficiently fixed on the plate-like carrier 10 in the stacking process of the buildup layer 110, and on the other hand, easy peelability between the prepreg 30 and the plate-like carrier 10 is ensured after the stacking process of the buildup layer 110. It is desirable to set the peel strength between the plate-like carrier 10 and the prepreg 30 (or the build-up layer 110 including the prepreg 30) based on the viewpoint. In addition, adjustment of peeling strength can be adjusted with the setting of the material and thickness of the above-mentioned mold release agent layer 20, and can be adjusted with the surface treatment of the plate-shaped carrier 10 or the prepreg 30.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm or more, preferably 30 gf / cm or more, more preferably 50 gf / cm or more. , Typically 200 gf / cm or less, preferably 150 gf / cm or less, more preferably 80 gf / cm or less.
- the peelability between the build-up layer 110 including the plate-like carrier 10 and the prepreg 30 can be ensured after the step of laminating the up layer 110.
- the peel strength between the plate carrier 10 and the prepreg 30 may be understood to be equal to the peel strength between the plate carrier 10 and the buildup layer 110.
- the peel strength between the plate-like carrier 10 and the prepreg 30 does not vary greatly even after the build-up layer 110 is laminated. Thereby, it can be ensured that the peelability between the buildup layer 110 including the plate carrier 10 and the prepreg 30 is not impaired even after the buildup layer 110 is laminated.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf / cm.
- the peel strength between the plate carrier 10 and the prepreg 30 is typically 10 gf
- the peel strength between the plate-like carrier 10 and the prepreg 30 after heating the base substrate 100 under the condition of 220 ° C. is 3 hours and 6 hours later from the viewpoint of securing the width of the number of the buildup layers 110 to be stacked. It is preferable that the peel strength satisfies the above-mentioned range both at 6 hours and after 9 hours, and it is more preferable that all the peel strengths after 3 hours, 6 hours and 9 hours satisfy the above-mentioned range.
- the peel strength is measured in accordance with a 90 degree peel strength measuring method defined in JIS C6481.
- the peel strength between the resin layer and the copper foil is desired to be high, for example, the matte surface (M surface) of the electrolytic copper foil is used as the adhesive surface with the resin layer, and surface treatment such as roughening treatment is performed.
- the adhesion strength is improved by a chemical and physical anchor effect.
- various binders are added on the resin layer side in order to increase the adhesive strength with the copper foil.
- the plate-like carrier 10 and the prepreg 30 are finally peeled, and therefore it is not desirable that the peel strength is excessively high.
- the surface roughness of the bonded surface was measured on the upper surface of the plate-like carrier 10 measured according to JIS B 0601 (2001).
- point average roughness Rz jis
- it is preferably 3.5 ⁇ m or less, more preferably 3.0 ⁇ m or less.
- the surface roughness is preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more. From the viewpoint of adjusting the surface roughness, it is easy to use the glossy surface of the plate-like carrier 10 as the lamination surface of the release agent layer 20.
- the prepreg 30 does not contain a binder for increasing the adhesive force with the release agent layer 20.
- the wiring layer in the build-up layer 110 may use a metal foil, or may be formed using at least one of a subtractive method, a full additive method, or a semi-additive method.
- the subtractive method is a method of selectively removing unnecessary portions of metal foil on an arbitrary substrate such as a metal-clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like.
- the full additive method is a method of forming the wiring layer 50 that is a patterned conductor layer by using electroless plating and / or electrolytic plating.
- an electroless metal deposition and electrolytic plating, etching, or a combination of both are formed on a seed layer made of a metal foil, and then an unnecessary seed layer is etched away. This is a method for obtaining a conductor pattern.
- one or more of resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, metal foil with carrier, metal foil, or base substrate 100 may be included.
- a process of drilling holes in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, or a resin, and conducting conductive plating on the side and bottom surfaces of the hole Can further be included.
- the process of forming wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil constituting the metal foil with carrier is performed once. It can further include performing the above.
- a resin may be laminated on the patterned wiring layer 50, and a metal foil may be adhered to the resin.
- attach both surfaces to the said resin can also be further included.
- the “surface on which the wiring is formed” means a portion where wiring is formed on the surface that appears every time a buildup is performed, and the buildup substrate includes both a final product and an intermediate product.
- the metal foil with a carrier is obtained by laminating a metal foil on a resin or metal carrier functioning as a support substrate with a release agent layer interposed therebetween.
- the same material as the release agent layer 20 disclosed in the present application can be used for the release agent layer that releasably bonds between the carrier and the metal foil in the metal foil with a carrier.
- the laminate 150 may be diced in a state where the buildup layer 110 is laminated on the base substrate 100.
- the dicing depth does not have to be a level that completely separates the stacked body 150 and may be a level that does not reach the plate-like carrier 10.
- a groove that does not reach or reach the plate-like carrier 10 is provided.
- the equipment used for dicing is not limited to the type utilizing a dicing blade, and any method such as wire or laser can be adopted.
- the plate-like carrier 10 and the prepreg 30 may be separated and separated.
- the plate-like carrier 10 is not separated by dicing, a plurality of separated multilayer printed wiring boards can be obtained from the common plate-like carrier 10.
- the insulating layer 40 and the wiring layer 50 in the buildup layer 110 may be laminated by thermocompression bonding. This thermocompression bonding may be performed every time one layer is stacked, may be performed after being laminated to some extent, or may be performed all at once at the end.
- Via wiring may be formed in the buildup layer 110 in order to ensure electrical continuity between the wiring layers 50 in the buildup layer 110 or between the wiring layer 50 in the buildup layer 110 and external wiring.
- the process may be performed in the process of forming the buildup layer 110 on the base substrate 100, or may be performed after the buildup layers 110 having a predetermined number of layers are stacked on the base substrate 100.
- Via wiring may be formed in a state in which the buildup layer 110 is laminated on the base substrate 100, or the via wiring may be formed after the plate-like carrier 10 of the base substrate 100 is peeled from the buildup layer 110. good.
- a via hole that penetrates the upper wiring layer 50 and the intermediate insulating layer 40 and reaches the lower wiring layer 50 is formed.
- a conductive material is provided in the via hole by deposition or the like, thereby ensuring electrical conduction between the lower wiring layer 50 and the upper wiring layer 50.
- the via hole can be formed by any method such as mechanical cutting or laser processing.
- the number of insulating layers 40 through which the via hole passes is arbitrary, and may be two or more. Electrolytic plating may be used to fill the via hole with the conductive material.
- the base substrate 100 shown in FIG. 1 is prepared.
- the manufacturing method of the base substrate 100 itself is as described above.
- the release agent layer 20 is formed on the plate carrier 10, and then the prepreg 30 is formed into a plate shape via the release agent layer 20.
- the substrate 10 is mounted on the carrier 10 and heated and pressed from above to obtain the base substrate 100 in which the prepreg 30 is laminated on the plate-like carrier 10 via the release agent layer 20.
- the release agent layer 20 is formed with a constant layer thickness over the entire range of the upper surface of the plate-like carrier 10.
- the prepreg 30 is in close contact with the upper surface of the release agent layer 20 uniformly within a plane.
- a buildup layer 110 is laminated on the base substrate 100.
- the insulating layers 40 and the wiring layers 50 are alternately stacked.
- the number of stacked units composed of a set of the insulating layer 40 and the wiring layer 50 is typically 1 or more, and may be 2 or more, 3 or more, 4 or more.
- the increase in the number of laminated units makes it difficult to maintain the accuracy of the interlayer position of the multilayer printed wiring board.
- the prepreg 30 as the lowermost layer of the multilayer printed wiring board is stably fixed in advance on the base substrate 100, and the buildup layer 110 can be stably laminated on the prepreg 30. it can.
- the release agent layer 20 is separately protected. Therefore, it may be necessary to select the thickness and material of the release agent layer 20 in consideration of the relationship with this member.
- the prepreg 30 that is the lowermost layer of the buildup layer 110 can be laminated on the release agent layer 20 to avoid the above problems.
- the wiring layer 50 is, but not limited to, a metal foil or a patterned metal foil, and preferably a copper foil or a patterned copper foil.
- the wiring layer 50 may be formed by utilizing a normal semiconductor process technology.
- the wiring layer 50 is not intended to be particularly limited, but typically, a solid wiring layer formed by vapor deposition typified by CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition) is utilized by using photolithography technology. Is formed by patterning.
- the wiring layer 50 is not necessarily patterned, and the wiring layer 50 may be a solid wiring layer.
- the insulating layer 40 may come into contact with the prepreg 30 for the removed portion of the wiring layer by patterning. Patterning may be performed using lift-off technology.
- the insulating layer 40 is a resin layer provided with a resin layer or via wiring (interlayer wiring), but is not limited thereto, and can typically be exemplified by a thermosetting resin or a photosensitive resin.
- the insulating layer 40 may be a prepreg reinforced with glass fiber or an inorganic filler.
- the constituent resin of the insulating layer 40 may be selected from materials having the same or similar characteristics as the prepreg. You may form into a film using the application
- the insulating layer 40 is not particularly limited, but typically, an insulating material is formed by vapor deposition represented by CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition), and the like. Accordingly, conductive vias are provided to ensure electrical connection between the upper and lower wiring layers 50.
- the method for incorporating the conductive via into the insulating layer 40 is arbitrary.
- a mask layer having an opening is formed on the insulating layer 40 deposited on the wiring layer 50. Etching is performed through the mask layer to remove the insulating layer 40 in a range corresponding to the opening of the mask layer.
- a method of filling the conductive material in a range where 40 is removed can be exemplified.
- the wiring layer 50 is made of a conductive material such as copper, aluminum, or polysilicon.
- the insulating layer 40 is made of an insulating material such as silicon dioxide.
- the via incorporated in the insulating layer 40 is made of a conductive material such as copper, aluminum, or polysilicon.
- the constituent resin of the insulating layer 40 may be selected from materials having the same or similar characteristics as the prepreg 30.
- the laminate 120 and the buildup layer 110 in which the release agent layer 20 remains on the plate-like carrier 10 are separated.
- the laminate 120 and the buildup layer 110 may be separated by manually peeling them, but both may be separated using a robot or the like.
- the base substrate 100 shown in FIG. 1 may be manufactured by hot pressing another new prepreg 30 on the laminate 120 after the separation step shown in FIG. Thereafter, in the same manner as described above, the buildup layer 110 may be laminated as shown in FIG. 2, and the laminate 120 and the buildup layer 110 may be separated as shown in FIG.
- a desired number of prepregs, then a two-layer metal-clad laminate called “inner core”, then a prepreg, and further “metal foil with carrier” are laminated in order, and the unit of this laminate unit (Also referred to as “page”) may be repeatedly stacked about 10 times to form a press assembly (commonly referred to as “book”).
- the book is sandwiched between a pair of flat plates, set in a hot press machine, and press-molded at a predetermined temperature and pressure to produce a large number of four-layer metal-clad laminates simultaneously.
- a flat plate for example, a stainless plate can be used.
- the plate is not limited, for example, a thick plate of about 1 to 10 mm can be used.
- a metal-clad laminate having four or more layers can generally be produced in the same process by increasing the number of inner core layers.
- a step of adjusting the thickness by half-etching the entire surface of the metal foil constituting the wiring layer 50 may be included.
- Laser processing is performed at a predetermined position of the metal foil constituting the wiring layer 50 to form a via hole penetrating the metal foil and the resin, and after applying a desmear process for removing smear in the via hole, the bottom of the via hole, the side surface and the metal Electroless plating may be performed on the entire surface or a part of the foil to form an interlayer connection, and further electrolytic plating may be performed as necessary.
- a plating resist may be formed in advance on each portion of the metal foil where electroless plating or electrolytic plating is unnecessary before performing each plating.
- the surface of the metal foil may be chemically roughened in advance.
- the plating resist is removed after plating.
- a circuit is formed by removing unnecessary portions of the metal foil and the electroless plating portion and the electrolytic plating portion by etching. In this way, a build-up substrate can be manufactured.
- the process from the lamination of the resin and the copper foil to the circuit formation may be repeated a plurality of times to form a multilayer build-up substrate.
- the top layer of the buildup layer 110 may be provided with a metal foil with a carrier in which a metal foil is adhered to one side of a resin carrier substrate.
- the carrier substrate of the metal foil with carrier may be a lower layer than the metal foil, or vice versa.
- a metal foil with a carrier in which a metal foil is adhered to both surfaces of a resin carrier substrate may be laminated.
- Another base substrate 100 may be laminated on the top layer of the buildup layer 110.
- a prepreg containing a thermosetting resin may be used as the insulating layer 40 of the buildup layer 110.
- the insulating layer 40 is a resin layer, for example, a prepreg or a photosensitive resin.
- a prepreg is used as the insulating layer 40
- a via hole may be provided in the prepreg by laser processing. After the laser processing, desmear treatment for removing smear in the via hole is preferably performed.
- a photosensitive resin is used as the resin
- the resin in the via hole forming portion can be removed by a photolithography method.
- electroless plating is performed on the bottom and side surfaces of the via hole, the entire surface or a part of the resin to form an interlayer connection, and further electrolytic plating is performed as necessary.
- a plating resist may be formed in advance on each portion of the resin where electroless plating or electrolytic plating is unnecessary before performing each plating. Further, when the adhesion between electroless plating, electrolytic plating, plating resist and resin is insufficient, the surface of the resin may be chemically roughened in advance. When a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the electroless plating portion or the electrolytic plating portion by etching.
- FIG. 4 is a schematic cross-sectional view of the base substrate.
- FIG. 5 is a schematic cross-sectional view showing a state in which build-up layers are laminated on both surfaces of a base substrate.
- the release agent layer 20 and the prepreg 30 are sequentially laminated also on the lower surface of the plate-like carrier 10. Even in such a case, the same effect as the first embodiment can be obtained.
- the buildup layers 110 can be laminated on both surfaces of the plate-like carrier 10, and the utilization efficiency of the base substrate 100 can be effectively increased. The production efficiency of the multilayer printed wiring board can be increased.
- the thickness of the release agent layer 20 attached to both surfaces of the plate-like carrier 10 may be the same or different. This also applies to the prepreg 30 disposed in the upper layer and the lower layer of the plate-like carrier 10. The same applies to the configuration of the buildup layer 110 formed in the upper layer and the lower layer of the base substrate 100.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
- a laminate comprising the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product, which are used alone or in combination.
- the release agent layer has the following formula: Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
- a laminate comprising: an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product shown in FIG.
- a laminate in which a release agent layer is laminated on at least one main surface of a metal plate carrier A laminate in which the release agent layer is a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin.
- Example- ⁇ Experimental example 1> Prepare a rolled copper foil (thickness 70 ⁇ m), and apply nickel-zinc (Ni-Zn) alloy plating treatment and chromate (Cr-Zn chromate) treatment to the both sides of the both surfaces.
- the average roughness (Rz cis: measured in accordance with JIS B 0601 (2001)) was set to 1.5 ⁇ m.
- Nickel-zinc alloy plating Ni concentration 17g / L (added as NiSO 4 ) Zn concentration 4g / L (added as ZnSO 4 ) pH 3.1 Liquid temperature 40 °C Current density 0.1-10A / dm 2 Plating time 0.1 to 10 seconds
- an aqueous solution of the release agent was applied using a spray coater, and then the copper foil surface was dried in air at 100 ° C.
- the use conditions of the release agent the type of release agent, the stirring time from when the release agent is dissolved in water to before application, the concentration of the release agent in the aqueous solution, the alcohol concentration in the aqueous solution, the pH of the aqueous solution Is shown in the table of FIG.
- a prepreg having a thickness of 200 ⁇ m (manufactured by Nanya Plastic Co., Ltd., FR-4 prepreg) was laminated on both sides of the copper foil with a release agent layer thus obtained to obtain a base substrate.
- the hot press conditions were a pressure of 30 kg / mm 2 , a temperature of 170 ° C., and a holding time of 100 minutes.
- a prepreg manufactured by Nanya Plastic Co., FR-4 prepreg, thickness 62 ⁇ m
- a copper foil manufactured by JX Nippon Mining & Metals Co., Ltd., JTC
- a thickness of 12 ⁇ m was laminated by hot pressing to form a build-up layer.
- the hot press conditions are the same as when the above-mentioned base substrate was obtained. Assuming that a heat history is applied to the laminate comprising the base substrate and the buildup layer thus obtained during further heat treatment such as buildup layer formation, the conditions described in the table shown in FIG.
- the formation of the release material resin coating on the S surface in Experimental Example 11 was performed using a doctor blade after applying a resin coating composition having the composition shown in the table of FIG. 6 by the gravure coating method. The thickness was adjusted to 2-4 ⁇ m. Moreover, the applied resin coating film was baked by heating at 150 ° C. for 30 seconds.
- bisphenol A type epoxy resin is used as the epoxy resin shown in the table of FIG. 6
- methyl ether melamine resin is used as the melamine resin
- polytetrafluoroethylene is used as the fluororesin
- dimethyl silicone resin is used. Used dimethylpolysiloxane.
- Example 12 FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metals, JTC 12 ⁇ m (product name)) are sequentially stacked on both sides of the same base substrate as in Examples 1 to 11. Hot pressing was performed under a predetermined heating condition at a pressure of 3 MPa to prepare a four-layer copper-clad laminate.
- a 100 ⁇ m diameter hole penetrating the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine.
- electroless copper plating on the copper foil surface on the copper foil with carrier exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate, and copper plating by electrolytic copper plating The electrical connection was formed between the copper foil on the copper foil with a carrier and the copper foil on the surface of the four-layer copper-clad laminate.
- a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. In this way, a four-layer buildup substrate was obtained.
- the main surface of the plate carrier is typically the upper surface or the lower surface thereof.
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Abstract
Description
前記第3工程により得られた前記多層プリント配線基板上に前記第1樹脂層とは異なる第2樹脂層、及び更なるビルドアップ層を積層する第4工程を更に含む、と良い。
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、と良い。
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、と良い。
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、と良い。
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、と良い。
前記離型剤層が、次式:
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる。
前記離型剤層が、次式:
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる。
前記離型剤層が、シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜である。
図1乃至図3を参照して第1実施形態について説明する。図1は、ベース基材の概略的な断面図である。図2は、ベース基材上にビルドアップ層を積層した状態を示す概略的な工程図である。図3は、多層プリント配線基板と板状キャリアを剥離する工程を模式的に示す工程図である。
Ni濃度 17g/L(NiSO4として添加)
Zn濃度 4g/L(ZnSO4として添加)
pH 3.1
液温 40℃
電流密度 0.1~10A/dm2
めっき時間 0.1~10秒
Cr濃度 1.4g/L(CrO3又はK2CrO7として添加)
Zn濃度 0.01~1.0g/L(ZnSO4として添加)
Na2SO4濃度 10g/L
pH 4.8
液温 55℃
電流密度 0.1~10A/dm2
めっき時間 0.1~10秒
離型剤層20の構成材料は、本願に開示、若しくは現時点において入手可能なものに限定されるべきものではないが、例えば、次の化学式に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせを離型剤層20に活用すると良い。
上述のシラン化合物に代えて、分子内に2つ以下のメルカプト基を有する化合物を離型剤層20に活用しても良い。この例としては、チオール、ジチオール、チオカルボン酸又はその塩、ジチオカルボン酸又はその塩、チオスルホン酸又はその塩、及びジチオスルホン酸又はその塩が挙げられ、これらの中から選択される少なくとも一種を用いることができる。
次式に示す構造を有するアルミネート化合物、チタネート化合物、ジルコネート化合物、又はその加水分解生成物質、又は該加水分解生成物質の縮合体(以下、単に金属アルコキシドと記述する)を単独で又は複数混合して使用して、板状キャリア10とプリプレグ30を貼り合わせることで、適度に密着性が低下し、剥離強度を後述するような範囲に調節できる。
これらの炭化水素基は一つ以上の水素原子がハロゲン原子で置換されてもよく、例えば、フッ素原子、塩素原子、又は臭素原子で置換されることができる。
シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜を使用して、板状キャリア10とプリプレグ30を貼り合わせることで、適度に密着性が低下し、剥離強度を後述するような範囲に調節できる。
塗布工程は、コーティング対象物(板状キャリア10及びプリプレグ30の少なくとも一方)に、主剤としてのシリコーンと、硬化剤としてのエポキシ系樹脂、メラミン系樹脂と、必要に応じて離型剤としてのフッ素樹脂とからなる樹脂塗料を塗布して樹脂塗膜を形成する工程である。樹脂塗料は、アルコール等の有機溶媒にエポキシ系樹脂、メラミン系樹脂、フッ素樹脂及びシリコーンを溶解したものである。また、樹脂塗料における配合量(添加量)は、シリコーン100質量部に対して、エポキシ系樹脂、メラミン系樹脂の合計が10~1500質量部であることが好ましい。また、フッ素樹脂は、シリコーン100質量部に対して、0~50質量部であることが好ましい。
焼付け工程は、塗布工程で形成された樹脂塗膜に125~320℃(焼付け温度)で0.5~60秒間(焼付け時間)の焼付け処理を施す工程である。このように、所定配合量の樹脂塗料で形成された樹脂塗膜に所定条件の焼付け処理を施すことによって、樹脂塗膜により付与された物(例えば、板状キャリア10)と他方の物(例えば、プリプレグ30)との間の剥離強度が所定範囲に制御される。本発明において、焼付け温度はプリプレグ30の到達温度である。また、焼付け処理に使用される加熱手段としては、従来公知の装置を使用する。
図4及び図5を参照して第2実施形態について説明する。図4は、ベース基材の概略的な断面図である。図5は、ベース基材の両面上にビルドアップ層を積層した状態を示す概略的な断面図である。本実施形態においては、図4に示すように、板状キャリア10の下面上にも離型剤層20、プリプレグ30を順に積層する。このような場合であっても第1実施形態と同様の効果を得ることができる。本構成の場合、図5に模式的に示すように板状キャリア10の両面にビルドアップ層110を積層することができ、ベース基材100の利用効率を効果的に高めることができ、結果として多層プリント配線基板の製造効率を高めることができる。
上述の説明から明らかなように、本願には上述のベース基材の製造に用いられる積層体も開示されており、詳細には、次のとおりのものである。
前記離型剤層が、次式:
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、積層体。
前記離型剤層が、分子内に2つ以下のメルカプト基を有する化合物を用いてなる、積層体。
前記離型剤層が、次式:
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、積層体。
前記離型剤層が、シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜である、積層体。
<実験例1>
圧延銅箔(厚さ70μm)を準備し、その両面に対して、下記の条件によるニッケル-亜鉛(Ni-Zn)合金めっき処理及びクロメート(Cr-Znクロメート)処理を施し、両面面の十点平均粗さ(Rz jis:JIS B 0601(2001)に準拠して測定)を1.5μmとした。
Ni濃度 17g/L(NiSO4として添加)
Zn濃度 4g/L(ZnSO4として添加)
pH 3.1
液温 40℃
電流密度 0.1~10A/dm2
めっき時間 0.1~10秒
Cr濃度 1.4g/L(CrO3又はK2CrO7として添加)
Zn濃度 0.01~1.0g/L(ZnSO4として添加)
Na2SO4濃度 10g/L
pH 4.8
液温 55℃
電流密度 0.1~10A/dm2
めっき時間 0.1~10秒
図6の表に示す銅箔、樹脂(プリプレグ)及び離型剤を用いて、実験例1と同様の手順で、ベース基材とビルドアップ層からなる積層体を作製した。それぞれについて実験例1と同様の評価を行った。結果を図6の表に示す。
実施例1~11と同様のベース基材の両側に、FR-4プリプレグ(南亜プラスティック社製)、銅箔(JX日鉱日石金属(株)製、JTC12μm(製品名))を順に重ね、3MPaの圧力で所定の加熱条件にてホットプレスを行い、4層銅張積層板を作製した。
10 板状キャリア
20 離型剤層
30 プリプレグ
110 ビルドアップ層
Claims (38)
- 金属製の板状キャリアの少なくとも1つの主面上に離型剤層を介して樹脂層が積層したベース基材を準備する第1工程と、
前記ベース基材の前記樹脂層上に1層以上のビルドアップ層を積層する第2工程と、
を含む多層プリント配線基板の製造方法。 - 前記板状キャリアの基板厚が、5μm以上1600μm以下である、請求項1に記載の多層プリント配線基板の製造方法。
- 前記板状キャリアと前記樹脂層間の剥離強度が、10gf/cm以上200gf/cm以下である、請求項1又は2に記載の多層プリント配線基板の製造方法。
- 220℃で3時間、6時間又は9時間のうちの少なくとも一つの加熱後における、前記板状キャリアと前記樹脂層間の剥離強度が、10gf/cm以上200gf/cm以下である、請求項1乃至3の何れか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層が積層された前記樹脂層と前記板状キャリアとを分離する第3工程を更に含む、請求項1乃至4の何れか一項に記載の多層プリント配線基板の製造方法。
- 前記樹脂層を第1樹脂層とする請求項5に記載の多層プリント配線基板の製造方法にして、
前記第3工程により得られた前記多層プリント配線基板上に前記第1樹脂層とは異なる第2樹脂層、及び更なるビルドアップ層を積層する第4工程を更に含む、多層プリント配線基板の製造方法。 - 前記樹脂層が、プリプレグである、請求項1乃至6のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記樹脂層は、120~320℃のガラス転移温度Tgを有する、請求項1乃至7のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層が、1以上の絶縁層と1以上の配線層を含む、請求項1乃至8のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層に含まれる1以上の配線層が、パターニングされた若しくはパターニングされていない金属箔である、請求項1乃至9のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層に含まれる1以上の絶縁層が、プリプレグである、請求項1乃至10のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層が、片面あるいは両面金属張積層板を含む、請求項1乃至11のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層が、サブトラクティブ法又はフルアディティブ法又はセミアディティブ法の少なくとも一方を用いて形成される、請求項1乃至12のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ベース基材上に前記ビルドアップ層が積層した積層体に対してダイシング処理を施す第5工程を更に含む、請求項1乃至13のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記ダイシング処理により、前記ベース基材上に前記ビルドアップ層が積層した前記積層体には1以上の溝が形成され、当該溝により前記ビルドアップ層が個片化可能である、請求項14に記載の多層プリント配線基板の製造方法。
- 前記ビルドアップ層に含まれる1以上の絶縁層に対してビア配線を形成する第6工程を更に含む、請求項1乃至15のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記離型剤層が、次式:
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、請求項1乃至16のいずれか一項に記載の多層プリント配線基板の製造方法。 - 前記離型剤層が、分子内に2つ以下のメルカプト基を有する化合物を用いてなる、請求項1乃至16のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記離型剤層が、次式:
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、請求項1乃至16のいずれか一項に記載の多層プリント配線基板の製造方法。 - 離型剤層が、シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜である、請求項1乃至16のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記板状キャリアが銅又は銅合金からなる請求項1乃至20のいずれか一項に記載の多層プリント配線基板の製造方法。
- 前記配線層が銅又は銅合金からなる請求項1乃至21のいずれか一項に記載の多層プリント配線基板の製造方法。
- 請求項1乃至22の何れか一項に記載の多層プリント配線基板の製造方法により製造された多層プリント配線基板。
- 多層プリント配線基板の製造方法に用いられるベース基材であって、
金属製の板状キャリアと、
前記板状キャリアの少なくとも1つの主面上に形成された離型剤層と、
前記離型剤層を介して前記板状キャリア上に積層した樹脂層と、を備え、
前記樹脂層と前記板状キャリアとが剥離可能である、ベース基材。 - 前記板状キャリアの基板厚が、5μm以上1600μm以下である、請求項24に記載のベース基材。
- 前記板状キャリアと前記樹脂層間の剥離強度が、10gf/cm以上200gf/cm以下である、請求項24又は25に記載のベース基材。
- 220℃で3時間、6時間又は9時間のうちの少なくとも一つの加熱後における、前記板状キャリアと前記樹脂層間の剥離強度が、10gf/cm以上200gf/cm以下である、請求項24乃至26の何れか一項に記載のベース基材。
- 前記板状キャリアが銅又は銅合金からなる請求項24乃至27のいずれか一項に記載のベース基材。
- 前記樹脂層がプリプレグからなる請求項24乃至28のいずれか一項に記載のベース基材。
- 前記離型剤層が、次式:
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、請求項24乃至29のいずれか一項に記載のベース基材。 - 前記離型剤層が、分子内に2つ以下のメルカプト基を有する化合物を用いてなる、請求項24乃至29のいずれか一項に記載のベース基材。
- 前記離型剤層が、次式:
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、請求項24乃至29のいずれか一項に記載のベース基材。 - 離型剤層が、シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜である、請求項24乃至29のいずれか一項に記載のベース基材。
- 金属製の板状キャリアの少なくとも1つの主面上に離型剤層が積層された積層体であって、
前記離型剤層が、次式:
に示すシラン化合物、その加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、積層体。 - 金属製の板状キャリアの少なくとも1つの主面上に離型剤層が積層された積層体であって、
前記離型剤層が、分子内に2つ以下のメルカプト基を有する化合物を用いてなる、積層体。 - 金属製の板状キャリアの少なくとも1つの主面上に離型剤層が積層された積層体であって、
前記離型剤層が、次式:
に示すアルミネート化合物、チタネート化合物、ジルコネート化合物、これらの加水分解生成物、該加水分解生成物の縮合体を単独で又は複数組み合わせて用いてなる、積層体。 - 金属製の板状キャリアの少なくとも1つの主面上に離型剤層が積層された積層体であって、
前記離型剤層が、シリコーンと、エポキシ系樹脂、メラミン系樹脂及びフッ素樹脂から選択されるいずれか1つ又は複数の樹脂とで構成される樹脂塗膜である、積層体。 - 前記板状キャリアが銅又は銅合金からなる請求項34乃至37のいずれか一項に記載の積層体。
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KR20170109684A (ko) | 2017-09-29 |
JPWO2014054811A1 (ja) | 2016-08-25 |
TW201436686A (zh) | 2014-09-16 |
KR101980993B1 (ko) | 2019-05-21 |
JP6393619B2 (ja) | 2018-09-19 |
CN104685980A (zh) | 2015-06-03 |
CN104685980B (zh) | 2018-11-23 |
TWI571193B (zh) | 2017-02-11 |
TW201717724A (zh) | 2017-05-16 |
TWI631883B (zh) | 2018-08-01 |
KR20150059781A (ko) | 2015-06-02 |
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