WO2014046259A1 - Feuille métallique ayant un porteur - Google Patents

Feuille métallique ayant un porteur Download PDF

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Publication number
WO2014046259A1
WO2014046259A1 PCT/JP2013/075563 JP2013075563W WO2014046259A1 WO 2014046259 A1 WO2014046259 A1 WO 2014046259A1 JP 2013075563 W JP2013075563 W JP 2013075563W WO 2014046259 A1 WO2014046259 A1 WO 2014046259A1
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WIPO (PCT)
Prior art keywords
metal foil
carrier
resin
metal
group
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PCT/JP2013/075563
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English (en)
Japanese (ja)
Inventor
晃正 森山
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Jx日鉱日石金属株式会社
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Priority to JP2014536945A priority Critical patent/JP6104261B2/ja
Publication of WO2014046259A1 publication Critical patent/WO2014046259A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K2203/12—Using specific substances
    • H05K2203/121—Metallo-organic compounds
    • 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
    • H05K3/007—Manufacture or processing of a substrate for a printed circuit board supported by a temporary or sacrificial carrier

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 an aluminate compound, titanate compound or zirconate compound.
  • 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: 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • Metal foil with a carrier in any one of. (10) The metal foil with a carrier according to any one of (1) to (9), wherein the metal foil is a copper foil. (11) On the surface of the metal foil, the following formula:
  • 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: 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr
  • the metal foil for printed wiring boards which has the aluminate compound,
  • the ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the carrier is 0.4 ⁇ m or more and 10.0 ⁇ m or less, according to any one of (11) to (13)
  • Metal foil for printed wiring boards is 0.4 ⁇ m or more and 10.0 ⁇ m or less, according to any one of (11) to (13)
  • Metal foil for printed wiring boards is 0.4 ⁇ m or more and 10.0 ⁇ m or less, according to any one of (11) to (13)
  • Metal foil for printed wiring boards is 0.4 ⁇ m or more and 10.0 ⁇ m or less
  • 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: 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • a metal foil having an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product, either alone or in combination, and a resin plate on the surface Metal foil used for mechanically releasably adhering a cylindrical carrier.
  • 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: 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • a resinous plate-like carrier having the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensates of the hydrolysis products alone or in combination. (20) On at least one surface, the following formula:
  • 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: 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 R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • 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 (10), 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: (22) A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (10), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to (10) A metal foil with a carrier according to any one of the above, or a method for producing a multilayer metal-clad laminate comprising repeatedly laminating a metal foil one or more times.
  • 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 (23).
  • 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 metal foil with a carrier according to any one of (1) to (10).
  • 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 (10), and then resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate , (1) to (10)
  • 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 with carrier which further includes performing the process of forming wiring in at least one of metal foil which comprises, and at least one of metal foil.
  • 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.
  • an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, a condensation product of the hydrolysis product (hereinafter simply referred to as “ 11b), which is described as “metal alkoxide”.
  • 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 adjusting a metal alkoxide (aluminate compound, titanate compound, zirconate compound or a hydrolysis product thereof, or a hydrolysis product thereof having a structure represented by the following formula:
  • a metal alkoxide aluminate compound, titanate compound, zirconate compound or a hydrolysis product thereof, or a hydrolysis product thereof having a structure represented by the following formula:
  • the condensate is used alone or in combination. This is because such metal alkoxide is bonded between the plate-like carrier and the metal foil, whereby the adhesiveness is appropriately lowered and the peel strength can be adjusted to the above-described range.
  • 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 or 1 or 2, m is an integer from 1 to M, and R1 At least one of these 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 (a hydrocarbon in which one or more hydrogen atoms are substituted with a halogen atom). It preferably has one or two groups).
  • 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 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 applying the metal alkoxide in the molecule to the bonding surface of the metal foil and / or plate carrier, the B-stage resin plate carrier is applied to the bonding surface of the metal foil. It can be manufactured by hot press lamination.
  • 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 peel strength between the metal foil and the plate carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and 50 gf / cm. While it is more preferably at least cm, it is preferably at most 200 gf / cm, more preferably at most 150 gf / cm, and even more preferably at most 80 gf / cm.
  • 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.
  • a metal plate has been used as a plate-shaped carrier of a metal foil with a carrier.
  • the plate-like carrier and the metal foil are adhered to each other by welding or adhesion.
  • an adhesive from the viewpoint of heat resistance, there are many things that are generally not suitable for build-up, and when closely contacting by welding, the peel strength is too high when using full-surface welding, It is difficult to peel off easily, and it becomes difficult to prevent the chemical solution from entering between the plate-shaped carrier and the metal foil when using partial welding. . Therefore, by using a resin-made plate-like carrier, an appropriate peel strength can be exhibited with the metal foil, and by using a heat-resistant resin, it can sufficiently withstand the heat history during build-up. be able to.
  • the plate-like carrier preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimal range, for example, a glass transition temperature Tg of 120 to 320 ° C., preferably 170 to 240 ° C. It is.
  • 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 ⁇ m or more, preferably 5 ⁇ m or more, and 400 ⁇ m or less, preferably 120 ⁇ 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 applies the above metal alkoxide to at least one surface of the metal foil as described above, which serves as the adhesion surface, in order to adhere the resin-made plate carrier in a peelable manner.
  • the surface of the metal foil may be subjected to the chromate treatment as described above before applying the metal alkoxide.
  • the present invention provides a plate-like carrier having the above metal alkoxide on at least one surface of the plate-like carrier that serves as an adhesion 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 metal alkoxide is coated on the surface of the metal foil as described above.
  • the surface of the metal foil may be subjected to the chromate treatment as described above before being coated with the metal alkoxide.
  • the surface of the metal foil or resin was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), Al, If Ti and Zr are detected, it can be inferred that the metal alkoxide is present on the surface of the metal foil or resin.
  • XPS X-ray photoelectron spectrometer
  • EPMA electron beam microanalyzer
  • EDX energy dispersive X-ray analysis
  • Al aluminum
  • 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 once or more, for example, A method for producing a multilayer metal-clad laminate comprising repeatedly laminating 1 to 10 times is provided.
  • the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired.
  • a book different from the resin, single-sided or double-sided metal-clad laminate, and the first metal foil with carrier is used. It can be arbitrarily selected from the group consisting of the metal foil with carrier of the invention and the metal foil.
  • 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.
  • a resin is laminated on the metal foil side of the metal foil with carrier described above, and then 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 Is provided one or more times, for example, 1 to 10 times, and a buildup substrate manufacturing method is provided.
  • the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired.
  • the resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the first metal with carrier It can be arbitrarily selected from the group consisting of the metal foil with a carrier of the present invention different from the foil and the metal foil.
  • 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 hole is formed 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, a metal foil, or a resin.
  • the method may further include a step of opening and conducting conductive plating on a side surface and a 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 formed in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil or a resin, and conductive plating is performed on the side and bottom surfaces of the hole. Further, a metal foil and a circuit portion constituting the single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a method for producing a build-up board at least once including the step of forming a circuit on the metal foil I will provide a.
  • the metal foil with carrier used here is the metal foil with carrier 11 in which the metal 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 metal-clad laminate called inner layer core 13, then prepreg 12, and further metal foil 11 with 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. Are laminated in order.
  • a step of half-etching the entire surface of the metal foil to adjust the thickness may be included.
  • 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 When a plating resist is used, the plating resist is removed after plating. Next, 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 containing a thermosetting resin can be suitably used as the resin plate used for manufacturing the build-up substrate.
  • 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.
  • the via hole can be formed by laser processing. After the laser processing, desmear treatment for removing smear in the via hole is preferably performed.
  • 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 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 wiring is formed on the surface through a plating process and / or an etching process, and further, build-up wiring is performed by separating and separating between the carrier resin and the metal foil.
  • the 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.
  • 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 16 In Experimental Example 1, when the copper foil and the prepreg were bonded together, copper with a carrier was used under the same conditions as in Experimental Example 1 except that neither the glossy surface of the copper foil nor the prepreg was treated with a metal alkoxide. A foil 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.
  • the metal alkoxide is processed on the surface of the copper foil or the surface of the prepreg, and if it is processed under the same conditions with the same compound, the subsequent laminate It was found that the same results were obtained in the peel strength, the peel strength after heating, and the peelability.
  • 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)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)

Abstract

L'invention porte sur une feuille métallique ayant un porteur, dans laquelle feuille la résistance à l'arrachage d'un porteur en forme de feuille en résine et d'une feuille métallique a été régulée. La feuille métallique ayant un porteur, qui comprend un porteur en résine en forme de feuille et une feuille métallique qui a été amenée à adhérer de façon détachable à au moins une surface du porteur, est caractérisée en ce que le porteur en forme de feuille et la feuille métallique sont liés à l'aide d'un composé d'aluminate, d'un composé de titanate, d'un composé de zirconate, de produits hydrolysés de ceux-ci, ou de produits de condensation des produits hydrolysés, structurés de façon spécifique, soit indépendamment soit en combinaison les uns avec les autres.
PCT/JP2013/075563 2012-09-20 2013-09-20 Feuille métallique ayant un porteur WO2014046259A1 (fr)

Priority Applications (1)

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JP2012207449 2012-09-20
JP2012-207449 2012-09-20

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JPWO2014054811A1 (ja) * 2012-10-04 2016-08-25 Ｊｘ金属株式会社 多層プリント配線基板の製造方法及びベース基材
JPWO2014054803A1 (ja) * 2012-10-04 2016-08-25 Ｊｘ金属株式会社 多層プリント配線基板の製造方法及びベース基材

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JPH0647755A (ja) * 1992-07-28 1994-02-22 Matsushita Electric Works Ltd 銅張り積層板の製造方法
JP2002033581A (ja) * 2000-07-13 2002-01-31 Mitsui Mining & Smelting Co Ltd 銅張積層板の製造方法
WO2002024444A1 (fr) * 2000-09-22 2002-03-28 Circuit Foil Japan Co., Ltd. Feuille de cuivre pour carte de connexions ultrafine haute densite
JP2005502496A (ja) * 2001-09-06 2005-01-27 オリン コーポレイション 低いプロフィールの結合向上を有する銅箔
WO2007135972A1 (fr) * 2006-05-19 2007-11-29 Mitsui Mining & Smelting Co., Ltd. Feuille de cuivre pourvue d'une feuille de support, procÉdÉ de fabrication associÉ, feuille de cuivre traitÉe en surface pourvue d'une feuille de support, et stratifiÉ cuivrÉ utilisant la feuille de cuivre traitÉe en surface pourvue d'une feuille de support
JP2009272589A (ja) * 2008-05-12 2009-11-19 Nippon Mining & Metals Co Ltd キャリヤー付金属箔
WO2012108070A1 (fr) * 2011-02-10 2012-08-16 フリージア・マクロス株式会社 Combinaison d'une feuille métallique et d'un support et procédé de production d'un substrat stratifié l'utilisant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0647755A (ja) * 1992-07-28 1994-02-22 Matsushita Electric Works Ltd 銅張り積層板の製造方法
JP2002033581A (ja) * 2000-07-13 2002-01-31 Mitsui Mining & Smelting Co Ltd 銅張積層板の製造方法
WO2002024444A1 (fr) * 2000-09-22 2002-03-28 Circuit Foil Japan Co., Ltd. Feuille de cuivre pour carte de connexions ultrafine haute densite
JP2005502496A (ja) * 2001-09-06 2005-01-27 オリン コーポレイション 低いプロフィールの結合向上を有する銅箔
WO2007135972A1 (fr) * 2006-05-19 2007-11-29 Mitsui Mining & Smelting Co., Ltd. Feuille de cuivre pourvue d'une feuille de support, procÉdÉ de fabrication associÉ, feuille de cuivre traitÉe en surface pourvue d'une feuille de support, et stratifiÉ cuivrÉ utilisant la feuille de cuivre traitÉe en surface pourvue d'une feuille de support
JP2009272589A (ja) * 2008-05-12 2009-11-19 Nippon Mining & Metals Co Ltd キャリヤー付金属箔
WO2012108070A1 (fr) * 2011-02-10 2012-08-16 フリージア・マクロス株式会社 Combinaison d'une feuille métallique et d'un support et procédé de production d'un substrat stratifié l'utilisant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014054811A1 (ja) * 2012-10-04 2016-08-25 Ｊｘ金属株式会社 多層プリント配線基板の製造方法及びベース基材
JPWO2014054803A1 (ja) * 2012-10-04 2016-08-25 Ｊｘ金属株式会社 多層プリント配線基板の製造方法及びベース基材

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