WO2013183606A1 - Feuille métallique fixée à un support - Google Patents

Feuille métallique fixée à un support Download PDF

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Publication number
WO2013183606A1
WO2013183606A1 PCT/JP2013/065407 JP2013065407W WO2013183606A1 WO 2013183606 A1 WO2013183606 A1 WO 2013183606A1 JP 2013065407 W JP2013065407 W JP 2013065407W WO 2013183606 A1 WO2013183606 A1 WO 2013183606A1
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WIPO (PCT)
Prior art keywords
metal foil
carrier
group
resin
plate
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PCT/JP2013/065407
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English (en)
Japanese (ja)
Inventor
倫也 古曳
晃正 森山
Original Assignee
Jx日鉱日石金属株式会社
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Filing date
Publication date
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to JP2014519989A priority Critical patent/JP6013474B2/ja
Priority to KR1020177019931A priority patent/KR20170086690A/ko
Priority to CN201380029157.0A priority patent/CN104334346B/zh
Priority to KR1020197001782A priority patent/KR20190009427A/ko
Priority to KR20147036813A priority patent/KR20150024353A/ko
Publication of WO2013183606A1 publication Critical patent/WO2013183606A1/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
    • 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
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • 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
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • 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
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0147—Carriers and holders
    • H05K2203/0156—Temporary polymeric carrier or foil, e.g. for processing or transferring
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4682—Manufacture of core-less build-up multilayer circuits on a temporary carrier or on a metal foil

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 by 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 inventors By treating with a silane compound, the inventors have found the possibility of realizing peel strength according to a desired application, and completed the present invention.
  • R 1 is an alkoxy group or a halogen atom
  • R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
  • Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.
  • R 1 is an alkoxy group or a halogen atom
  • R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
  • Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms).
  • R 1 is an alkoxy group or a halogen atom
  • R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
  • Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms).
  • R 1 is an alkoxy group or a halogen atom
  • R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
  • Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms).
  • 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 (7), 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: (16) 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 (7), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to ( 7) A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier according to any one of 1) or a metal foil repeatedly 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 (18) 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 (17).
  • a method for producing a buildup substrate comprising a step of forming one or more buildup wiring layers on at least one metal foil side of the metal foil with carrier according to any one of (1) to (7).
  • 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 (7), and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, (1)
  • 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
  • a step of laminating the metal foil with a carrier according to any one of (1) to (7), wherein the metal foil is in close contact with the surface on which the wiring is formed, and contacting the resin plate side A method for manufacturing a build-up substrate according to any one of (22) to (24).
  • 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 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 silane compound 11b described later.
  • 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 the silane compound represented by the following formula, a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a silane compound). It is performed by using alone or in combination. This is because, by sticking the plate-like carrier and the metal foil using the silane compound, 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 hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.
  • the silane compound must have at least one alkoxy group.
  • a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom
  • a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much.
  • the silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom.
  • the alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.
  • the silane compound has three alkoxy groups and the hydrocarbon group (a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom). It is preferable to have one).
  • both R 3 and R 4 are alkoxy groups.
  • Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group and the like, straight chain, branched or cyclic carbon number of 1-20, preferably carbon number of 1-10, more preferably carbon number of 1- 5 alkoxy groups.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group examples include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, and n-hexyl.
  • cycloalkyl group examples include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, which have 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms.
  • An alkyl group is mentioned.
  • the aryl group includes a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, etc., having 6 to 20, preferably 6 to 14 carbon atoms.
  • an alkyl group eg, tolyl group,
  • one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.
  • Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo-pentyl.
  • propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of availability.
  • 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 the silane compound is applied to the bonding surface of the metal foil and / or plate carrier, the B-stage resin plate carrier is hot-press laminated on the bonding surface of the metal foil. Can be manufactured.
  • the silane compound 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 silane compound is used.
  • the stirring time after the silane compound is dissolved in water can be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is a method of using without stirring.
  • the concentration of the silane compound in the aqueous solution of the silane compound can be 0.01 to 10.0% by volume, and typically 0.1 to 5.0% by volume.
  • the pH of the aqueous solution of the silane compound 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 before use of the silane compound is preferably 10 gf / cm or more, and preferably 30 gf / cm or more. 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 even more preferably 80 gf / cm or less.
  • the peel strength between the metal foil and the plate carrier in such a range, the peel strength 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 ⁇ 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 and Ti are contained in the chromate treatment solution
  • Chromate treatment 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 the above-mentioned silane compound, its hydrolyzate, on at least one surface of the metal foil as described above, which becomes the adhesion surface, in order to allow the resinous plate-like carrier to be adhered in a peelable manner.
  • a metal foil having a decomposition product or a condensation product of the hydrolysis product.
  • the silane compound, the hydrolysis product thereof or the condensation product of the hydrolysis product a part or all of the surface of the metal foil is coated with the silane compound. It is possible by acting. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before acting with the silane compound.
  • the present invention provides the above-described silane compound, its hydrolysis product, or at least one surface of the plate-like carrier serving as the adhesion surface, in order to adhere the metal foil as described above in a peelable manner.
  • a plate-like carrier having a condensate of the hydrolysis product is provided.
  • a part or all of the surface of the plate-like carrier is coated with the silane compound. It is possible to act by such as.
  • the present invention provides a metal for a coreless multilayer printed wiring board in which the surface of a metal foil as described above is provided with the silane compound, a hydrolyzed product thereof, or a condensate of the hydrolyzed product.
  • a metal foil as described above is provided with the silane compound, a hydrolyzed product thereof, or a condensate of the hydrolyzed product.
  • Provide foil in order to give the surface of the metal foil the silane compound, the hydrolysis product thereof or the condensation product of the hydrolysis product, a part or all of the surface of the metal foil is coated with the silane compound. It is possible by making it act. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before acting on the silane compound.
  • the surface of the metal foil or resin was measured with a scanning electron microscope or the like equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis). If detected, it can be inferred that a silane compound 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
  • 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, 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.
  • 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, or 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.
  • 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 can be manufactured.
  • 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 can be manufactured.
  • 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.
  • the wiring is formed on the surface through the plating process and / or the etching process, and further, the build-up wiring is separated and separated between the carrier resin and the copper 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.
  • Example 1 A plurality of electrolytic copper foils (thickness 12 ⁇ m) were prepared, and nickel-zinc (Ni—Zn) alloy plating treatment and chromate (Cr—Zn) were performed on the shiny (S) surface of each electrolytic copper foil under the following conditions. (Chromate) treatment, the ten-point average roughness (measured in accordance with JIS B 0601: 2001) of the bonded surface (here, S surface) is 1.5 ⁇ m, and the resin is Mitsubishi Gas Chemical Co., Ltd. A company-prepared prepreg (BT resin) was bonded to the S surface of the electrolytic copper foil and hot-pressed at 190 ° C. for 100 minutes to prepare a copper foil with a carrier.
  • BT resin company-prepared prepreg
  • Nickel-zinc alloy plating Ni concentration 17g / L (added as NiSO 4 ) Zn concentration 4g / L (added as ZnSO 4 ) pH 3.1 Liquid temperature 40 °C Current density 0.1-10A / dm 2 Plating time 0.1 to 10 seconds
  • an aqueous solution of a silane compound is applied to the S surface using a spray coater, and then the copper foil surface is dried in air at 100 ° C., and then bonded to a prepreg. went.
  • Table 1 shows the type of silane compound, the stirring time from when the silane compound is dissolved in water to before application, the concentration of the silane compound in the aqueous solution, the alcohol concentration in the aqueous solution, and the pH of the aqueous solution. Show.
  • the types of copper foil bonding surfaces, surface treatment conditions and surface roughness Rz jis, silane compound usage conditions, prepreg types, and copper foil and prepreg lamination conditions are as shown in Table 1. is there.
  • Treatment liquid 3-glycidoxypropyltrimethoxysilane 0.9 volume% aqueous solution pH 5.0 to 9.0 Stirred at room temperature for 12 hours
  • Treatment method After applying the treatment liquid using a spray coater, the treated surface is dried in air at 100 ° C. for 5 minutes.
  • Example 19 to 20> A copper foil with a carrier shown in Table 3 was prepared in the same procedure as in Experimental Example 1 using a silane compound as a copper foil and a resin (prepreg). Further, heat treatment was performed under the conditions shown in Table 3. Evaluation similar to Experimental example 1 was performed about the copper foil with a carrier obtained in this way. The results are shown in Tables 3 and 4.
  • the S surface was used as the bonding surface of the copper foil, and the surface was chromated under the above-described conditions.
  • the surface roughness Rz cis of the copper foil, the type of prepreg, the use conditions of the silane compound for the surface treatment of the prepreg, and the lamination conditions of the copper foil and the prepreg are as shown in Table 3.
  • 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.
  • the resin was destroyed at the time of build-up during the peeling operation of the copper foil in the carrier-attached copper foil, or the resin remained on the copper foil surface without being peeled off.
  • the resin was peeled off without being destroyed during the copper foil peeling operation in the carrier-added copper foil during build-up, but the copper foil was removed without peeling operation. Sometimes peeled off.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

L'invention concerne une feuille métallique fixée à un support, dont la résistance à l'écaillage entre un support de résine du type plaque et une feuille métallique est ajustée. L'invention concerne une feuille métallique fixée à un support comprenant un support de résine du type plaque et une feuille métallique fixée à au moins une surface du support de manière pelable, le support du type plaque et la feuille métallique étant adhérés l'un à l'autre par utilisation d'un composé de silane prédéterminé.
PCT/JP2013/065407 2012-06-04 2013-06-03 Feuille métallique fixée à un support WO2013183606A1 (fr)

Priority Applications (5)

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JP2014519989A JP6013474B2 (ja) 2012-06-04 2013-06-03 キャリア付金属箔
KR1020177019931A KR20170086690A (ko) 2012-06-04 2013-06-03 캐리어 부착 금속박
CN201380029157.0A CN104334346B (zh) 2012-06-04 2013-06-03 附载体金属箔
KR1020197001782A KR20190009427A (ko) 2012-06-04 2013-06-03 캐리어 부착 금속박
KR20147036813A KR20150024353A (ko) 2012-06-04 2013-06-03 캐리어 부착 금속박

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JP2012-127567 2012-06-04
JP2012127567 2012-06-04

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KR (3) KR20150024353A (fr)
CN (1) CN104334346B (fr)
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WO (1) WO2013183606A1 (fr)

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JPWO2013183604A1 (ja) * 2012-06-04 2016-02-01 Jx日鉱日石金属株式会社 多層プリント配線板の製造方法
JPWO2013183605A1 (ja) * 2012-06-04 2016-02-01 Jx日鉱日石金属株式会社 キャリア付金属箔
JPWO2013183607A1 (ja) * 2012-06-04 2016-02-01 Jx日鉱日石金属株式会社 キャリア付金属箔
WO2017110404A1 (fr) * 2015-12-25 2017-06-29 三井金属鉱業株式会社 Feuille de cuivre avec support, feuille de cuivre avec résine et procédé de fabrication de carte de circuit imprimé

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TWI621381B (zh) * 2014-04-02 2018-04-11 Jx Nippon Mining & Metals Corp Laminated body with metal foil with carrier
JP6438370B2 (ja) * 2015-08-03 2018-12-12 Ｊｘ金属株式会社 プリント配線板の製造方法、表面処理銅箔、積層体、プリント配線板、半導体パッケージ及び電子機器
JP6498091B2 (ja) * 2015-09-25 2019-04-10 Ｊｘ金属株式会社 表面処理金属箔、積層体、プリント配線板、半導体パッケージ、電子機器

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WO2017110404A1 (fr) * 2015-12-25 2017-06-29 三井金属鉱業株式会社 Feuille de cuivre avec support, feuille de cuivre avec résine et procédé de fabrication de carte de circuit imprimé
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Also Published As

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JP6013474B2 (ja) 2016-10-25
TWI519413B (zh) 2016-02-01
CN104334346B (zh) 2017-05-03
JPWO2013183606A1 (ja) 2016-02-01
KR20150024353A (ko) 2015-03-06
KR20170086690A (ko) 2017-07-26
KR20190009427A (ko) 2019-01-28
TW201410448A (zh) 2014-03-16
CN104334346A (zh) 2015-02-04

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