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WO2014024878A1 - Feuille métallique à support - Google Patents

Feuille métallique à support Download PDF

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Publication number
WO2014024878A1
WO2014024878A1 PCT/JP2013/071241 JP2013071241W WO2014024878A1 WO 2014024878 A1 WO2014024878 A1 WO 2014024878A1 JP 2013071241 W JP2013071241 W JP 2013071241W WO 2014024878 A1 WO2014024878 A1 WO 2014024878A1
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WO
WIPO (PCT)
Prior art keywords
metal foil
carrier
resin
metal
plate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/071241
Other languages
English (en)
Japanese (ja)
Inventor
晃正 森山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to JP2014529508A priority Critical patent/JP6205361B2/ja
Publication of WO2014024878A1 publication Critical patent/WO2014024878A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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

Definitions

  • the present invention relates to a metal foil with a carrier. More specifically, the present invention relates to a metal foil with a carrier used in the production of a single-sided or two-layer multilayer board or an ultra-thin coreless substrate used for a printed wiring board.
  • a printed wiring board uses, as a basic constituent material, a dielectric material called “prepreg” obtained by impregnating a base material such as a synthetic resin plate, a glass plate, a glass nonwoven fabric, and paper with a synthetic resin. . Further, a sheet such as copper or copper alloy foil having electrical conductivity is bonded to the side facing the prepreg.
  • the laminated body thus assembled is generally called a CCL (CopperoppClad Laminate) material.
  • the surface of the copper foil in contact with the prepreg is usually a mat surface in order to increase the bonding strength.
  • a foil made of aluminum, nickel, zinc or the like may be used instead of the copper or copper alloy foil. Their thickness is about 5 to 200 ⁇ m. This commonly used CCL (Copper Clad Laminate) material is shown in FIG.
  • Patent Document 1 proposes a metal foil with a carrier composed of a synthetic resin plate-shaped carrier and a metal foil that is mechanically peelably adhered to at least one surface of the carrier. Describes that it can be used for the assembly of printed wiring boards. It was shown that the peel strength between the plate-like carrier and the metal foil is preferably 1 gf / cm to 1 kgf / cm. According to the metal foil with a carrier, since the copper foil is supported over the entire surface by the synthetic resin, generation of wrinkles on the copper foil during lamination can be prevented. In addition, since the metal foil with carrier is in close contact with the synthetic resin without gaps, when the surface of the metal foil is plated or etched, it can be put into the chemical solution for plating or etching. .
  • the linear expansion coefficient of the synthetic resin is at the same level as the copper foil that is a constituent material of the substrate and the prepreg after polymerization, the circuit is not misaligned, resulting in fewer defective products, It has the outstanding effect that a yield can be improved.
  • the metal foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to reducing the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield, but the peel strength between the plate-like carrier and the metal foil.
  • a remarkable problem for the inventor is that the peel strength between the plate-like carrier and the metal foil becomes too high depending on the material of the plate-like carrier, and means for easily adjusting the peel strength is provided. It is desirable.
  • this invention makes it a subject to provide the metal foil with a carrier in which the peeling strength of resin-made plate-shaped carrier and metal foil was adjusted.
  • the present inventors have a predetermined structure on at least one surface prior to the bonding between the resin plate and the metal foil.
  • the present inventors completed the present invention by finding the possibility of realizing a peel strength according to a desired application by coating with a compound having a mercapto group.
  • the present invention is as follows. (1) A metal foil with a carrier made of a resinous plate-like carrier and a metal foil that is detachably adhered to at least one surface of the carrier, and the plate-like carrier and the metal foil are in the molecule. Metal foil with a carrier formed by bonding using a compound having two or less mercapto groups. (2) The compound having two or less mercapto groups in the molecule is composed of thiol, dithiol, thiocarboxylic acid or salt thereof, dithiocarboxylic acid or salt thereof, thiosulfonic acid or salt thereof, and dithiosulfonic acid or salt thereof.
  • the metal foil with a carrier according to (1) which is at least one selected from the group consisting of: (3) The metal foil with a carrier according to (1) or (2), wherein the peel strength between the plate-like carrier and the metal foil is 10 gf / cm or more and 200 gf / cm or less.
  • the ten-point average roughness (Rz jis) of the surface of the metal foil that is not in contact with the carrier is 0.4 ⁇ m or more and 10.0 ⁇ m or less, according to any one of (1) to (7) Metal foil with carrier.
  • the compound having two or less mercapto groups in the molecule is composed of 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.
  • a metal foil having a compound having two or less mercapto groups in the molecule on at least one surface the metal foil being used in such a manner that a resinous plate-like carrier is peelably adhered to the surface.
  • Foil. The compound having two or less mercapto groups in the molecule is composed of 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.
  • the compound having two or less mercapto groups in the molecule is composed of 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.
  • a resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (11), and then the resin or the metal foil is repeatedly laminated one or more times.
  • a method for producing a multilayer metal-clad laminate comprising: (26) A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (11), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to (11)
  • the multilayer metal-clad laminate further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier.
  • a manufacturing method of a board The method for producing a multilayer metal-clad laminate comprising the step of removing a part or all of the separated and separated metal foil by etching in the production method according to (27).
  • a method for manufacturing a buildup board comprising a step of forming one or more buildup wiring layers on the metal foil side of the laminate according to any one of (1) to (11).
  • a single-sided or double-sided wiring board In the method for manufacturing a buildup board according to (32), 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
  • substrate which further includes the process of drilling a hole in and carrying out conductive plating to the side surface and bottom face of the said hole.
  • 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 with carrier The manufacturing method of the buildup board
  • the peel strength between the plate carrier and the metal foil can be easily adjusted. Therefore, for example, a metal foil with a carrier that has conventionally exhibited an excessively high peel strength is adjusted to a preferable peel strength, so that an advantage of improving the productivity of a printed wiring board using the metal foil with a carrier is obtained. .
  • CCL An example of the configuration of CCL is shown.
  • the structural example of the metal foil with a carrier which concerns on this invention is shown.
  • the assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined to the single side
  • the assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined on both surfaces of the resin board) is shown.
  • a metal foil with a carrier comprising a resin-made plate-like carrier and a metal foil that is detachably adhered to one or both sides, preferably both sides of the carrier.
  • a metal foil with a carrier according to the present invention is shown in FIGS.
  • the metal foil with carrier 11 in which the metal foil 11a is detachably adhered to both surfaces of a resin plate carrier 11c is shown at the beginning of FIG.
  • the plate-like carrier 11c and the metal foil 11a are bonded together using a compound having two or less mercapto groups in the molecule described later or a salt 11b thereof.
  • the metal foil with a carrier of the present invention has a structure in which the metal foil and the resin are finally separated and can be easily peeled off. In this respect, since the CCL is not peeled off, the structure and function are completely different.
  • the metal foil with carrier used in the present invention must be peeled off eventually, it is inconvenient that the adhesiveness is excessively high, but the plate-like carrier and the metal foil are chemicals such as plating performed in the printed circuit board manufacturing process. Adhesiveness that does not peel in the processing step is necessary.
  • the adjustment of the peel strength for realizing such adhesion is performed by using a compound having two or less mercapto groups in the molecule or a salt thereof. This is because by using such a compound or a salt thereof between the plate-like carrier and the metal foil and bonding them together, the adhesiveness is appropriately reduced and the peel strength can be adjusted to the above-described range.
  • a compound having three or more mercapto groups in the molecule or a salt thereof is bonded between a plate carrier and a metal foil, it is not suitable for the purpose of reducing the peel strength described in the present application.
  • Examples of the compound having two or less mercapto groups in the molecule 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. At least one selected from these can be used.
  • 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.
  • the metal foil with carrier can be manufactured by bringing a plate-like carrier and metal foil into close contact with each other by hot pressing. For example, after a metal foil and / or a plate-like carrier bonding surface is coated with a compound having two or less mercapto groups in the molecule, the metal foil bonding surface is made of a B-stage resin. This plate-shaped carrier can be manufactured by hot press lamination.
  • a compound having two or less mercapto groups in the molecule 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 compound having two or less mercapto groups in a highly hydrophobic molecule is used.
  • the peel strength can be adjusted by adjusting the concentration.
  • the concentration of the compound having 2 or less mercapto groups in the molecule in the aqueous solution can be 0.01 to 10.0% by weight, typically 0.1 to 5.0%. % By weight.
  • the pH of the aqueous solution of the compound having two or less mercapto groups in the molecule 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 peel strength between the metal foil and the plate-like carrier is preferably 10 gf / cm or more, preferably 30 gf / cm. More preferably, it is more preferably 50 gf / cm or more, while it is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and 80 gf / cm or less. Even more preferred.
  • the peel strength between the metal foil and the plate carrier is such that it can be easily peeled off by hand, that is, mechanically peeled off, without being peeled off during transport or processing. Easy to adjust.
  • the metal after assuming at least one of heating for 3 hours, 6 hours or 9 hours at 220 ° C., assuming heating conditions in the production process of the multilayer printed wiring board.
  • the peel strength between the foil and the plate-like carrier is preferably 30 gf / cm or more, and more preferably 50 gf / cm or more.
  • the peel strength is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and even more preferably 80 gf / cm or less.
  • the peel strength after heating at 220 ° C. was described above in both 3 hours and 6 hours, or both 6 hours and 9 hours from the viewpoint of being able to cope with various lamination numbers. It is preferable to satisfy the range, and it is further preferable that all peel strengths after 3 hours, 6 hours, and 9 hours satisfy the above-described range.
  • the peel strength is measured in accordance with a 90 degree peel strength measuring method defined in JIS C6481.
  • the resin that serves as the plate-like carrier is not particularly limited, and phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used, but a thermosetting resin is preferable.
  • a prepreg can also be used. The prepreg before being bonded to the metal foil is preferably in a B-stage state.
  • the linear expansion coefficient of the prepreg (C stage) is 12 to 18 ( ⁇ 10 ⁇ 6 / ° C.), 16.5 ( ⁇ 10 ⁇ 6 / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 ( ⁇ 10 ⁇ 6 / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultra-thin coreless substrate.
  • the prepreg used here may be the same as or different from the prepreg constituting the circuit board.
  • the plate-like carrier preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimum range, for example, a glass transition temperature Tg of 120 to 320 ° C., preferably 170 to 240 ° C. .
  • the glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).
  • the thermal expansion coefficient of the resin is within + 10% and ⁇ 30% of the thermal expansion coefficient of the metal foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the metal foil and the resin, thereby reducing the occurrence of defective products and improving the yield.
  • the thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin, it will bend and will not flow through the printed wiring board manufacturing process. Therefore, it is usually 5 ⁇ m or more and 1000 ⁇ m or less, preferably 50 ⁇ m or more and 900 ⁇ m or less, and more preferably 100 ⁇ m or more and 400 ⁇ m or less.
  • the metal foil copper or copper alloy foil is a typical one, but foil of aluminum, nickel, zinc or the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used.
  • the metal foil generally has a thickness of 1 [mu] m or more, preferably 5 [mu] m or more, and 400 [mu] m or less, preferably 120 [mu] m or less, considering use as a wiring of a printed circuit board.
  • metal foils having the same thickness may be used, or metal foils having different thicknesses may be used.
  • the metal foil used may be subjected to various surface treatments.
  • 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 not only affects the peel strength between the metal foil and the plate carrier, but also the chromate treatment 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.
  • the matte surface (M surface) of the electrolytic copper foil is used as an adhesive surface with the resin, and surface treatment such as roughening treatment is performed.
  • the adhesive strength is improved by the chemical and physical anchoring effects.
  • various binders are added to increase the adhesive strength with the metal foil.
  • the surface roughness of the bonded surface is JIS B 0601: in order to adjust the peel strength between the metal foil and the plate-like carrier to the preferred range described above.
  • the ten-point average roughness (Rz jis) of the metal foil surface measured according to 2001 it is preferably 3.5 ⁇ m or less, more preferably 3.0 ⁇ m or less.
  • Rz jis ten-point average roughness
  • the metal foil When electrolytic copper foil is used as the metal foil, it is possible to use either a glossy surface (shiny surface, S surface) or a rough surface (matte surface, M surface) by adjusting to such a surface roughness. However, it is easier to adjust the surface roughness by using the S-plane. On the other hand, it is preferable that the ten-point average roughness (Rz jis) of the surface of the metal foil not contacting the carrier is 0.4 ⁇ m or more and 10.0 ⁇ m or less.
  • the surface treatment for improving the peel strength such as roughening treatment is not performed on the bonding surface of the metal foil with the resin.
  • the binder for improving the adhesive force with metal foil is not added in resin.
  • the present invention provides two in the above molecule on at least one surface of the metal foil as described above, which becomes the adhesion surface.
  • a metal foil coated with the following compound having a mercapto group is provided.
  • the surface of the metal foil may be subjected to the chromate treatment as described above before coating with a compound having two or less mercapto groups in the molecule.
  • the present invention provides a plate-like carrier having a compound having two or less mercapto groups in the above molecule on at least one surface of the plate-like carrier to be a close contact surface of the metal foil.
  • This plate-like carrier can be suitably used for applications in which the metal foil as described above is adhered in a peelable manner.
  • the present invention provides a metal foil for a coreless multilayer printed wiring board in which the surface of the metal foil as described above is coated with a compound having two or less mercapto groups in the molecule. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before being coated with a compound having two or less mercapto groups in the molecule.
  • the surface of the metal foil or resin is measured with an apparatus such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), and S is If detected, it can be inferred that a compound having two or less mercapto groups in the molecule exists on the surface of the metal foil or resin.
  • XPS X-ray photoelectron spectrometer
  • EPMA electron beam microanalyzer
  • EDX energy dispersive X-ray analysis
  • this invention provides the use of the metal foil with a carrier mentioned above.
  • a multilayer metal comprising laminating a resin on at least one metal foil side of the above-described metal foil with carrier, and then laminating the resin or the metal foil repeatedly one or more times, for example, 1 to 10 times.
  • a method for producing a tension laminate is provided.
  • the resin is laminated on the metal foil side of the metal foil with carrier described above, and then the resin, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil is used once or more, for example, 1
  • a method for producing a multilayer metal-clad laminate comprising repeatedly laminating 10 times.
  • the above-described method for producing a multilayer metal-clad laminate can further include a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier.
  • the method may further include a step of removing a part or the whole of the metal foil by etching after the plate-like carrier and the metal foil are separated from each other.
  • the resin is laminated on the metal foil side of the metal foil with carrier described above, and then the resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil Provided is a method for manufacturing a build-up substrate, which includes repeatedly laminating at least once, for example, 1 to 10 times.
  • a method for manufacturing a buildup board including a step of laminating one or more buildup wiring layers on the metal foil side of the metal foil with carrier described above.
  • the build-up wiring layer can be formed using at least one of a subtractive method, a full additive method, and a semi-additive method.
  • the subtractive method is a method of forming a conductor pattern by selectively removing unnecessary portions of metal foil on a metal-clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like. Point to.
  • the full additive method is a method of forming a conductor pattern by electroless plating and / or electrolytic plating without using a metal foil for the conductor layer.
  • the semi-additive method is an electroless method on a seed layer made of metal foil, for example. In this method, a conductor pattern is formed by using metal deposition and electrolytic plating, etching, or a combination thereof, and then an unnecessary seed layer is removed by etching.
  • 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 may further include conducting conductive plating on the side surface and the bottom surface of the hole.
  • the step 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.
  • the manufacturing method of the build-up board may further include a step of bringing a metal foil into close contact with one surface on the surface on which the wiring is formed, and further laminating the carrier side of the metal foil with a carrier according to the present invention. . Moreover, it is possible to further include a step of laminating a metal foil with a carrier according to the present invention in which a resin is laminated on the surface on which the wiring is formed and the metal foil is adhered to both sides of the resin.
  • 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 manufacturing method of the build-up substrate may further include a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil.
  • each layer can be laminated
  • 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 collectively at the end.
  • the present invention provides a method for manufacturing a build-up board as described above, wherein a hole is made in a single-sided or double-sided wiring board, a single-sided or double-sided copper-clad laminate, a metal foil or a resin, and conductive plating is performed on the side and bottom surfaces of the hole. Further, the metal foil and circuit portion constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided copper-clad laminate, and the method for producing a build-up board at least including the step of forming a circuit on the metal foil I will provide a.
  • the metal foil with carrier used here is the copper foil with carrier 11 in which the copper foil 11a is adhered to one surface of the plate-like carrier 11c.
  • a desired number of prepregs 12, and then a two-layer printed circuit board or two-layer copper-clad laminate called an inner core 13, and then a prepreg 12 and then a copper foil 11 with a carrier 11 are sequentially stacked.
  • a set of four-layer CCL assembly units is completed.
  • the unit 14 (referred to as “page”) is repeated about 10 times to form a press assembly 15 (referred to as “book”) (FIG. 3).
  • the book 15 is sandwiched between the laminated molds 10 and set in a hot press machine, and a large number of four-layer CCLs can be manufactured simultaneously by press molding at a predetermined temperature and pressure.
  • a stainless plate can be used as the laminated mold 10.
  • the plate is not limited, for example, a thick plate of about 1 to 10 mm can be used.
  • CCL having four or more layers can be produced in the same process by increasing the number of inner core layers.
  • a resin as an insulating layer, a two-layer circuit board, a resin as an insulating layer are stacked in order, and the metal foil side is in contact with the resin plate on it, Furthermore, a buildup board
  • substrate can be manufactured by laminating
  • a resin or conductor layer as an insulating layer is provided on at least one metal foil side of the metal foil with a carrier in which the metal foil is adhered to both surfaces or one surface of the resinous plate-like carrier 11c.
  • a carrier in which the metal foil is adhered to both surfaces or one surface of the resinous plate-like carrier 11c.
  • holes are made in the circuit forming metal foil and resin plate, conductive plating is applied to the side and bottom surfaces of the holes to form vias, and this circuit forming metal is further formed.
  • a build-up substrate can also be manufactured by forming a circuit on the remaining portion of the foil by a patterning technique or the like. You may perform the process so far several times.
  • a step of half-etching the entire surface of the metal foil to adjust the thickness may be included.
  • laser processing is performed at a predetermined position of the laminated metal foil 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 foil
  • Electroless plating is performed on the entire surface or a part of the substrate 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 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. Thereby, a build-up substrate is obtained.
  • the steps 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 resin side of the metal foil of the metal foil with a carrier in which the metal foil is adhered to one side of the present invention may be contacted and laminated, or a resin plate is once laminated. Later, one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces of the present invention may be brought into contact with each other and laminated.
  • a prepreg can be used, and a prepreg containing a thermosetting resin can be preferably used.
  • a resin as an insulating layer such as a prepreg or a photosensitive layer is formed on the exposed surface of a metal foil of a laminate obtained by laminating a metal foil such as a copper foil on one or both sides of the plate carrier of the present invention. Laminating resin. Thereafter, a via hole is formed at a predetermined position of the resin.
  • prepreg is used as the resin
  • the via hole can be formed by laser processing or drilling. After the laser processing or drilling, desmear treatment for removing smear in the via hole may be performed.
  • a photosensitive resin is used as the resin, the resin in the portion where the via hole is formed can be removed by a photolithography method.
  • electroless plating is performed on the bottom and side surfaces of the via holes, the entire surface or a part of the resin to form interlayer connections, 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.
  • the plating resist is removed after plating. Next, an unnecessary portion of the electroless plating portion or the electrolytic plating portion is removed by etching to form a circuit. Thereby, a build-up substrate is obtained.
  • the steps from resin lamination to circuit formation may be repeated a plurality of times to form a multilayered build-up substrate. Further, the outermost surface of this build-up substrate is laminated by contacting the resin side of the laminate in which the metal foil is closely attached to one side of the present invention, or the resin side of the metal foil with a carrier having the metal foil closely attached to one side. Alternatively, after laminating the resin once, one metal foil of the laminate in which the metal foil is adhered to both surfaces of the present invention, or one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces May be laminated in contact with each other.
  • a multi-layer build-up is performed by forming a wiring on the surface through a plating process and / or an etching process, and further separating and separating between the carrier resin and the copper foil.
  • the wiring board is completed. Wiring may be formed on the peeling surface of the metal foil after peeling and separation, or the entire surface of the metal foil may be removed by etching to form a build-up wiring board.
  • a printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, a printed circuit board can be obtained even if an electronic component is mounted directly on a coreless buildup substrate before resin peeling.
  • the copper foil with a carrier was produced by processing.
  • 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
  • Example 20 In Experimental Example 1, when the copper foil and the prepreg were bonded together, the same conditions as in Experimental Example 1 were obtained except that the S surface of the copper foil was not treated with a compound having two or less mercapto groups in the molecule. Thus, a copper foil with a carrier was prepared, and the peel strength at each stage and the working time were evaluated. The respective results are shown in Table 1 and Table 2.
  • 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 two-layer build-up wiring boards were obtained by peeling off and separating the plate-like carrier of the copper foil with carrier and the copper foil.
  • the copper foil that was in close contact with the plate-like carrier on the two sets of two-layer build-up wiring boards was etched to form a wiring to obtain two sets of two-layer build-up wiring boards.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
PCT/JP2013/071241 2012-08-06 2013-08-06 Feuille métallique à support Ceased WO2014024878A1 (fr)

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JP2012174453 2012-08-06

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CN104943255A (zh) * 2014-03-25 2015-09-30 Jx日矿日石金属株式会社 表面处理铜箔、覆铜积层板、印刷配线板、电子机器、半导体封装及印刷配线板的制造方法
JP2015212426A (ja) * 2015-08-11 2015-11-26 Jx日鉱日石金属株式会社 表面処理銅箔、銅張積層板、プリント配線板、電子機器、半導体パッケージ、プリント配線板の製造方法、樹脂基材の製造方法、銅箔の表面プロファイルを樹脂基材に転写する方法及び樹脂基材
JP2016135924A (ja) * 2016-02-29 2016-07-28 Ｊｘ金属株式会社 表面処理銅箔、銅張積層板、プリント配線板の製造方法、半導体パッケージの製造方法及び電子機器の製造方法
WO2017022807A1 (fr) * 2015-08-03 2017-02-09 Ｊｘ金属株式会社 Procédé de fabrication de carte de circuit imprimé, feuille de cuivre traitée en surface, stratifié, carte de circuit imprimé, boîtier de semi-conducteur, et dispositif électronique
WO2017051897A1 (fr) * 2015-09-24 2017-03-30 Ｊｘ金属株式会社 Feuille métallique, feuille métallique pourvue d'une couche de démoulage, stratifié, carte de circuit imprimé, boîtier de semi-conducteur, dispositif électronique et procédé pour la production de carte de circuit imprimé
WO2023060864A1 (fr) * 2021-10-14 2023-04-20 深圳市汉嵙新材料技术有限公司 Feuille de cuivre souple ultra-mince présentant une ténacité élevée, son procédé de préparation et son utilisation
US20230257578A1 (en) * 2020-07-17 2023-08-17 Panasonic Intellectual Property Management Co., Ltd. Resin composition, prepreg, film provided with resin, metal foil provided with resin, metal-clad laminate, and wiring board
WO2023210285A1 (fr) * 2022-04-27 2023-11-02 株式会社ダイセル Corps assemblé et procédé de fabrication de corps assemblé

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JP2000156563A (ja) * 1998-11-19 2000-06-06 Matsushita Electric Ind Co Ltd プリント配線基板
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JP2003198123A (ja) * 2001-12-27 2003-07-11 Fujikura Ltd フレキシブルプリント配線基板
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104943255A (zh) * 2014-03-25 2015-09-30 Jx日矿日石金属株式会社 表面处理铜箔、覆铜积层板、印刷配线板、电子机器、半导体封装及印刷配线板的制造方法
JP2015183240A (ja) * 2014-03-25 2015-10-22 Jx日鉱日石金属株式会社 表面処理銅箔、銅張積層板、プリント配線板、電子機器、半導体パッケージ用回路形成基板、半導体パッケージ及びプリント配線板の製造方法
KR101902128B1 (ko) * 2014-03-25 2018-09-27 제이엑스금속주식회사 표면 처리 동박, 구리 피복 적층판, 프린트 배선판, 전자 기기, 반도체 패키지용 회로 형성 기판, 반도체 패키지 및 프린트 배선판의 제조 방법
WO2017022807A1 (fr) * 2015-08-03 2017-02-09 Ｊｘ金属株式会社 Procédé de fabrication de carte de circuit imprimé, feuille de cuivre traitée en surface, stratifié, carte de circuit imprimé, boîtier de semi-conducteur, et dispositif électronique
JP2015212426A (ja) * 2015-08-11 2015-11-26 Jx日鉱日石金属株式会社 表面処理銅箔、銅張積層板、プリント配線板、電子機器、半導体パッケージ、プリント配線板の製造方法、樹脂基材の製造方法、銅箔の表面プロファイルを樹脂基材に転写する方法及び樹脂基材
WO2017051897A1 (fr) * 2015-09-24 2017-03-30 Ｊｘ金属株式会社 Feuille métallique, feuille métallique pourvue d'une couche de démoulage, stratifié, carte de circuit imprimé, boîtier de semi-conducteur, dispositif électronique et procédé pour la production de carte de circuit imprimé
JPWO2017051897A1 (ja) * 2015-09-24 2018-08-30 Ｊｘ金属株式会社 金属箔、離型層付き金属箔、積層体、プリント配線板、半導体パッケージ、電子機器及びプリント配線板の製造方法
JP2016135924A (ja) * 2016-02-29 2016-07-28 Ｊｘ金属株式会社 表面処理銅箔、銅張積層板、プリント配線板の製造方法、半導体パッケージの製造方法及び電子機器の製造方法
US20230257578A1 (en) * 2020-07-17 2023-08-17 Panasonic Intellectual Property Management Co., Ltd. Resin composition, prepreg, film provided with resin, metal foil provided with resin, metal-clad laminate, and wiring board
WO2023060864A1 (fr) * 2021-10-14 2023-04-20 深圳市汉嵙新材料技术有限公司 Feuille de cuivre souple ultra-mince présentant une ténacité élevée, son procédé de préparation et son utilisation
WO2023210285A1 (fr) * 2022-04-27 2023-11-02 株式会社ダイセル Corps assemblé et procédé de fabrication de corps assemblé

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