WO2014054812A1 - Feuille métallique fixée à un support - Google Patents

Feuille métallique fixée à un support Download PDF

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Publication number
WO2014054812A1
WO2014054812A1 PCT/JP2013/077183 JP2013077183W WO2014054812A1 WO 2014054812 A1 WO2014054812 A1 WO 2014054812A1 JP 2013077183 W JP2013077183 W JP 2013077183W WO 2014054812 A1 WO2014054812 A1 WO 2014054812A1
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WIPO (PCT)
Prior art keywords
metal foil
carrier
group
metal
release agent
Prior art date
Application number
PCT/JP2013/077183
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English (en)
Japanese (ja)
Inventor
晃正 森山
倫也 古曳
雅史 石井
Original Assignee
Jx日鉱日石金属株式会社
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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 JP2014539857A priority Critical patent/JP6373189B2/ja
Publication of WO2014054812A1 publication Critical patent/WO2014054812A1/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
    • 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
    • B32B15/092—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 comprising epoxy resins
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]

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 multilayer laminated board in which two or more layers are laminated on one side or both sides used for a printed wiring board or an ultrathin coreless substrate.
  • 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 adhesive strength between the plate-like carrier and the metal foil is desirably 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.
  • Patent Document 2 describes a method for manufacturing a wiring board in which a build-up wiring layer is formed in a state where the build-up wiring layer can be peeled off on a temporary substrate, as in Patent Document 1.
  • a step of preparing a temporary substrate in which a glass nonwoven fabric is impregnated with a resin is prepared, and an outer peripheral portion of a wiring formation region on the temporary substrate is selectively provided with an adhesive layer on a peripheral side of the metal foil.
  • a wiring member in which the build-up wiring layer is formed on the metal foil by separating the metal foil from the temporary substrate by cutting an inner portion of the structure in which the wiring layer is formed. And a step of obtaining.
  • Patent Document 3 describes a manufacturing method in which a required wiring layer is formed on a temporary substrate so as to be peeled off, and then the wiring layer is separated from the temporary substrate to obtain a wiring substrate.
  • a base layer metal foil, release film, or release agent
  • a metal foil larger than the size of the base layer is in contact with an outer peripheral portion of the wiring formation region.
  • the metal foil is separated from the temporary substrate by cutting a portion corresponding to the peripheral edge of the base layer, thereby obtaining a wiring member in which the build-up wiring layer is formed on the metal foil. And having a degree.
  • the metal foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to the reduction of the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield.
  • the corner portion may collide with another member, and the plate-like carrier and the metal foil may be peeled off due to an external force applied at that time, resulting in a failure.
  • a chemical solution such as hydrochloric acid, sulfuric acid, hydrogen peroxide or permanganate may permeate from the interface between the copper foil with carrier and the plate carrier, and the metal foil may be peeled off from the plate carrier.
  • Patent Document 2 since the peripheral side of the metal foil is selectively bonded with the adhesive layer, the problem that the plate-like carrier is peeled off from the metal foil during handling can be alleviated. Is merely in contact with the plate-like carrier, there is a possibility that wrinkles will occur in the metal foil inside during handling. Considering the use of metal foil for wiring formation, the generation of wrinkles tends to lead to wiring defects, which is not preferable. Moreover, although the peripheral part of metal foil is adhere
  • Patent Document 3 the outer peripheral portion of the prepreg and the metal foil is bonded without specially using an adhesive layer. Moreover, there is no mention about the adhesive strength in that case. Therefore, the problem that the plate-like carrier and the metal foil are peeled off during handling cannot be solved.
  • an object of the present invention is to provide a metal foil with a carrier that can prevent peeling and wrinkle generation between a plate-like carrier and a metal foil during conveyance or processing (during handling).
  • the present inventors have effectively controlled peeling in handling by controlling the adhesive strengths in the plate carrier and the metal foil in the inner and outer peripheral parts to a certain range, respectively. It has been found that a metal foil with a carrier can be obtained, which can be prevented at the same time and the generation of wrinkles on the surface of the metal foil is also suppressed.
  • the present invention is as follows.
  • a metal foil with a carrier comprising a resin-made plate-like carrier and a metal foil laminated on at least one surface of the carrier, wherein the interface between the carrier and the metal foil is at least in the outer peripheral region.
  • the carrier and the metal foil are bonded with an adhesive strength of 201 to 1000 gf / cm through the adhesive layer at the corner, and the carrier and the metal foil are temporarily bonded with an adhesive strength of 10 to 200 gf / cm using a release agent in the remaining region.
  • Metal foil with carrier bonded.
  • the mold release agent has 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 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 wherein one or more hydrogen atoms are replaced by halogen atoms.
  • the mold release agent has 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 the valence of M, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • the metal foil with a carrier according to (1) containing the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensates of the hydrolysis products shown in (1).
  • the metal release foil according to (1) wherein the release agent contains silicone and one or more resins selected from an epoxy resin, a melamine resin, and a fluororesin.
  • the silane coupling agent used for forming the silane coupling agent layer has one or more of an epoxy group, an amino group, a methacryl group, and a vinyl group in the molecule.
  • Metal foil with carrier is one or more of an epoxy group, an amino group, a methacryl group, and a vinyl group in the molecule.
  • the ten-point average roughness (Rz jis) of the surface of the metal foil that is not in contact with the carrier is 0.4 ⁇ m or more and 10.0 ⁇ m or less, according to any one of (1) to (13) Metal foil with carrier.
  • the metal foil and the plate-like carrier after heating at 220 ° C.
  • a multilayer comprising laminating a resin on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (19), and then repeating the resin or the metal foil one or more times A method for producing a metal-clad laminate.
  • a resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (19), and then the resin, one-sided or double-sided metal-clad laminate, or the metal foil is once or more times A method for producing a multilayer metal-clad laminate comprising repeating.
  • a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil in the inner part after cutting, and a step of removing a part or all of the metal foil exposed by peeling by etching (22) The manufacturing method of the multilayer metal-clad laminate as described in (22).
  • (24) A multilayer metal-clad laminate obtained by the production method according to any one of (20) to (23).
  • (25) A method for manufacturing a buildup substrate, comprising a step of laminating 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 (19).
  • the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal with carrier The manufacturing method of the buildup board
  • the method further includes a step of laminating the carrier side of another metal foil with a carrier according to any one of (1) to (19), wherein a metal foil is adhered to one surface on the surface on which the wiring is formed (27 )-(29).
  • the mold release agent has 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 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 wherein one or more hydrogen atoms are replaced by halogen atoms.
  • the mold release agent has 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 the valence of M, At least one of R 1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
  • the metal according to any one of (37) to (42), comprising an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product shown in Foil.
  • the adhesive layer is at least one layer selected from a chromate layer and a silane coupling agent layer.
  • the silane coupling agent used for forming the silane coupling agent layer has one or more of an epoxy group, an amino group, a methacryl group, and a vinyl group in the molecule.
  • the metal foil with a carrier since the plate-like carrier and the metal foil are firmly bonded at the outer peripheral portion, peeling between the plate-like carrier and the metal foil during handling can be prevented. On the other hand, since the inside is appropriately bonded to such an extent that the plate-like carrier and the metal foil can be peeled off, wrinkles can be prevented from occurring in the metal foil during handling. Furthermore, according to a preferred embodiment of the present invention, since the plate-like carrier and the metal foil are firmly bonded to the entire outer peripheral portion, the effect of preventing the penetration of the chemical liquid into the interface is also high. Therefore, the handling property of the metal foil with carrier is improved, and the advantage that the productivity of the printed wiring board using the metal foil with carrier is improved is obtained.
  • CCL Configuration of CCL is shown. It is a typical top view of the metal foil in the previous stage which laminates
  • An assembly example of a four-layer metal-clad laminate using the carrier-attached copper foil according to the present invention is shown.
  • substrate using the copper foil with a carrier which concerns on this invention is shown.
  • a metal foil with a carrier is a metal foil with a carrier comprising a resin-made plate-like carrier and a metal foil laminated on at least one surface of the carrier, the carrier and the metal foil.
  • the carrier and the metal foil are bonded to each other through the adhesive layer at least at the corners in the outer peripheral region, and the carrier and the metal foil are temporarily bonded using the release agent in the remaining region. It is a foil.
  • the outer peripheral area refers to an area to be cut and removed later.
  • the interface between the carrier and the metal foil is firmly bonded via an adhesive layer at least at the four corners in the outer peripheral region, but is peeled off at other portions. It is bonded with moderate adhesive strength as much as possible. Therefore, even when the metal foil with a carrier is transported or when a multilayer laminated board or a build-up board is manufactured using this, the corner portion does not easily peel off even if it collides with other members. .
  • the metal foil with a carrier can be cut in the thickness direction at a portion inside the portion (adhesion region) where the carrier and the metal foil are bonded via an adhesive layer at an appropriate time such as after the end of conveyance.
  • the multilayer laminated board or the build-up board may be cut in the thickness direction at a portion inside the adhesive area. it can.
  • the carrier can be peeled off from the metal foil in a timely manner.
  • the timing at which the carrier is peeled off from the metal foil is not limited, but is usually after the formation of the multilayer laminate or the build-up substrate.
  • the multilayer laminate or the build-up substrate can be peeled off as necessary during the formation.
  • the exposed metal foil can be used as a conductive material for wiring formation.
  • the entire surface can be removed by etching or the like.
  • FIG. 2 a plan view of the metal foil 200 in the previous stage of laminating the plate-like carrier is schematically depicted here.
  • two opposing sides of the outer peripheral area of the metal foil 200 are areas where the adhesive layer is provided (adhesive area: 220).
  • the carrier and the metal foil are firmly bonded via the adhesive layer.
  • the inner remaining region is a region (temporary bonding region: 210) where the carrier and the metal foil are temporarily bonded using a release agent.
  • the four corners and the two opposite sides of the metal foil that are most likely to peel off are firmly bonded to the carrier by the adhesive layer, so that peeling during handling can be prevented.
  • the four sides of the outer peripheral region of the metal foil 200 are regions where the adhesive layer is provided (adhesive region: 220). In this region, the carrier and the metal foil are firmly bonded via the adhesive layer.
  • the inner remaining region surrounded by the adhesive layer region is a region (temporary bonding region: 210) where the carrier and the metal foil are temporarily bonded using a release agent.
  • the width of the adhesive region is sufficient to obtain a peeling prevention effect and a chemical solution penetration prevention effect.
  • the thickness is preferably 0.1 mm or more, more preferably 1.0 mm or more, and even more preferably 3.0 mm or more.
  • the width of the bonding region may be increased and about 1 to 10 holes having a diameter of about 0.01 mm to 10 mm may be provided using a drill or the like.
  • the hole provided in such an adhesion region can be used as a means for fixing a positioning pin or the like in the production of a multi-layer laminate described later or the build-up substrate.
  • it is preferably 50 mm or less, more preferably 25 mm or less, and 5 mm or less. Even more preferred.
  • a mode as shown in the right figure (c) of FIG. 2 is also possible.
  • four corners of the outer peripheral region of the metal foil 200 are regions where the adhesive layer is provided (adhesive region: 220). In this region, the carrier and the metal foil are firmly bonded via the adhesive layer.
  • the inner remaining region is a region (temporary bonding region: 210) where the carrier and the metal foil are temporarily bonded using a release agent. Even in this embodiment, the four corners of the metal foil that is most likely to peel off are firmly adhered to the carrier by the adhesive layer, and therefore peeling during handling can be prevented.
  • FIG. 3 schematically shows a side view according to an embodiment of the metal foil with carrier 230 according to the present invention.
  • the metal foil with carrier 230 according to the upper diagram (c) of FIG. 3 forms an adhesive layer on the entire bonding surface of the metal foil 200, and then coats a release agent on the inner temporary adhesive region to form a plate-like carrier. It can be produced by pasting the two sides of 240 by hot pressing or the like. Alternatively, a release agent is applied to the temporary adhesion regions 210 on both surfaces of the plate-like carrier 240, and then a metal foil 200 having an adhesive layer formed on the entire bonding surface is attached to both surfaces of the plate-like carrier 240 by hot pressing or the like. It can be produced by combining them.
  • the metal foil with carrier 230 forms an adhesive layer in the adhesion region 220 in the bonding surface of the metal foil 200, and applies a release agent to the temporary adhesion region, It can be manufactured by pasting the both sides of the plate-like carrier 240 by hot pressing or the like.
  • the outer bonded region (220) firmly bonded protects the inner temporary bonded region (210), so that the metal foil and the plate carrier in the temporary bonded region (210) can be separated. Infiltration of the chemical liquid into the interface between the metal foil and the plate carrier can be prevented.
  • the adhesive layer may be formed on any surface of the plate-like carrier and the metal foil.
  • the release agent may be applied to any surface of the plate-like carrier and the metal foil.
  • the adhesive layer may be formed on both the plate carrier and the metal foil.
  • the carrier and the metal foil are bonded via the adhesive layer, it is necessary to have a strong adhesive strength that does not easily peel off and also prevents the penetration of the chemical solution.
  • the carrier and the metal foil are bonded with an adhesive strength of 201 gf / cm or more, preferably 250 gf / cm or more, more preferably 350 gf / cm or more.
  • the carrier has an adhesive strength of 1000 gf / cm or less, preferably 750 gf / cm or less, more preferably 500 gf / cm or less. It is desirable that the metal foil is bonded.
  • the adhesive layer for realizing such adhesive strength examples include a chromate layer and a silane coupling agent layer. These may be used alone or in combination. Moreover, it is good also as a structure which laminated
  • the chromate layer can be formed by subjecting the bonding surface of the metal foil and / or plate-like carrier to chromate treatment. Since the chromate layer also has a rust prevention effect, it is preferable that at least the metal foil side be chromated. In order to increase the adhesive strength, the surface of the metal foil can be roughened.
  • the chromate layer when the chromate layer is immersed in an aqueous solution containing 0.1 to 10.0 g / L of hexavalent chromium ions for 1 to 60 seconds or the metal foil and the plate carrier are conductive These can be formed by electrolysis for 1 to 20 seconds using the above-mentioned aqueous solution as a cathode, and the silane coupling agent layer can be formed by, for example, using an aqueous solution containing 0.1 to 5.0% by volume of a silane coupling agent as a metal foil. Alternatively, it can be formed by spray coating on a plate-like carrier and then drying in air at 100 to 200 ° C.
  • silane coupling agent is not limited, but for example, the molecule has one or more of an epoxy group, amino group, methacryl group, or vinyl group as a reactive functional group, and methoxy as a hydrolyzable group. It is preferable to use a silane coupling agent having any one or more of a group, an ethoxy group, and a propoxy group.
  • the part where the carrier and the metal foil are temporarily bonded using a release agent must be peeled off, so it is inconvenient that the adhesiveness is excessively high. Adhesiveness that does not cause wrinkles or easily peel off in a chemical treatment process such as plating performed in the plate manufacturing process is necessary.
  • the carrier and the metal foil are bonded with an adhesive strength of 10 gf / cm or more, preferably 30 gf / cm or more, more preferably 50 gf / cm or more.
  • the carrier since it is not necessary to excessively increase the adhesive strength and the cost of the adhesive is increased, the carrier has an adhesive strength of 200 gf / cm or less, preferably 150 gf / cm or less, more preferably 80 gf / cm or less. It is desirable that the metal foil is bonded.
  • the adjustment of the adhesive strength for realizing such adhesion can be easily realized by using, for example, the following release agents (1) to (4).
  • Silane compound A silane compound having a structure represented by the following formula, a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a silane compound) is used alone or in combination. Then, by adhering the plate-like carrier and the metal foil, the adhesiveness is appropriately reduced, and the adhesive strength can be adjusted to a range as described later.
  • R 1 is an alkoxy group or a halogen atom
  • R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms
  • Any one of these 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 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.
  • By stirring the aqueous solution of the silane compound hydrolysis of the alkoxy group is promoted, and when the stirring time is long, condensation of the hydrolysis product is promoted.
  • the adhesive strength between the metal foil and the plate carrier tends to decrease when a silane compound that has undergone hydrolysis and condensation after a sufficient stirring time is used. Therefore, the adhesive strength can be adjusted by adjusting the stirring time.
  • 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. .
  • Examples of the compound having two or less mercapto groups in the molecule include thiol, dithiol, thiocarboxylic acid or a salt thereof, dithiocarboxylic acid or a salt thereof, thiosulfonic acid or a salt thereof, and dithiosulfonic acid or a salt thereof. At least one selected from the above can be used.
  • Thiol has one mercapto group in the molecule and is represented by, for example, R-SH.
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • Dithiol has two mercapto groups in the molecule and is represented by, for example, R (SH) 2 .
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • Two mercapto groups may be bonded to the same carbon, or may be bonded to different carbons or nitrogens.
  • the thiocarboxylic acid is one in which a hydroxyl group of an organic carboxylic acid is substituted with a mercapto group, and is represented by, for example, R—CO—SH.
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • the thiocarboxylic acid can also be used in the form of a salt. A compound having two thiocarboxylic acid groups can also be used.
  • Dithiocarboxylic acid is one in which two oxygen atoms in the carboxy group of an organic carboxylic acid are substituted with sulfur atoms, and is represented by, for example, R- (CS) -SH.
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • Dithiocarboxylic acid can also be used in the form of a salt.
  • a compound having two dithiocarboxylic acid groups can also be used.
  • the thiosulfonic acid is obtained by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, and is represented by, for example, R (SO 2 ) -SH.
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • thiosulfonic acid can be used in the form of a salt.
  • Dithiosulfonic acid is one in which two hydroxyl groups of organic disulfonic acid are substituted with mercapto groups, and is represented by, for example, R-((SO 2 ) -SH) 2 .
  • R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.
  • Two thiosulfonic acid groups may be bonded to the same carbon, or may be bonded to different carbons.
  • Dithiosulfonic acid can also be used in the form of a salt.
  • examples of the aliphatic hydrocarbon group suitable as R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.
  • alkyl group examples include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n And straight-chain or branched alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as -hexyl group, n-octyl group, and n-decyl group. .
  • cycloalkyl group is not limited, but it has 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., preferably 5 to 7 carbon atoms.
  • cycloalkyl group preferably 3 to 10 carbon atoms.
  • suitable aromatic hydrocarbon groups as R include phenyl groups, phenyl groups substituted with alkyl groups (eg, tolyl groups, xylyl groups), 1- or 2-naphthyl groups, anthryl groups, and the like. -20, preferably 6-14 aryl groups, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.
  • heterocyclic group suitable as R examples include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, which may contain either or both of a hydroxyl group and an amino group.
  • Preferred examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2, propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1-hexanol, 1- Octanethiol, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol, thiobenzoic acid, Examples include 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, and 2-mercapto-benzothiazole. Of these, 3-mercapto-1,2-propanediol is preferred from the viewpoint of water solubility and waste disposal.
  • the metal foil with carrier can be manufactured by bringing a plate-like carrier and metal foil into close contact with each other by hot pressing. For example, after a metal foil and / or a plate-like carrier bonding surface is coated with a compound having two or less mercapto groups in the molecule, the metal foil bonding surface is made of a B-stage resin. This plate-shaped carrier can be manufactured by hot press lamination.
  • a compound having two or less mercapto groups in the molecule can be used in the form of an aqueous solution.
  • Alcohols such as methanol and ethanol can be added in order to increase the solubility in water.
  • the addition of alcohol is particularly effective when a compound having two or less mercapto groups in a highly hydrophobic molecule is used.
  • the adhesive strength can be adjusted by adjusting the concentration.
  • the concentration of the compound having 2 or less mercapto groups in the molecule in the aqueous solution can be 0.01 to 10.0% by weight, typically 0.1 to 5.0%. % By weight.
  • the pH of the aqueous solution of the compound having two or less mercapto groups in the molecule is not particularly limited and can be used on either the acidic side or the alkaline side.
  • it can be used at a pH in the range of 3.0 to 10.0.
  • the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .
  • the adhesive strength between the metal foil and the plate-like carrier is preferably 10 gf / cm or more, preferably 30 gf / cm. More preferably, it is more preferably 50 gf / cm or more, while it is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and 80 gf / cm or less. Even more preferred.
  • the adhesive strength between the metal foil and the plate-shaped carrier in such a range, the adhesive strength can be easily adjusted so that it can be easily removed manually while it is not peeled off during transportation or processing.
  • Metal alkoxide An aluminate compound, titanate compound, zirconate compound having a structure represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a metal alkoxide) alone
  • a metal alkoxide aluminate compound, titanate compound, zirconate compound having a structure represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a metal alkoxide) alone
  • a metal alkoxide an adhesive strength suitable for temporary bonding can be easily obtained.
  • 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 R At least one of 1 is an alkoxy group.
  • M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.
  • the metal alkoxide must have at least one alkoxy group.
  • a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom
  • a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much.
  • the metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have 0-2. This is because when three or more hydrocarbon groups are present, the adhesion between the plate-like carrier and the metal foil surface tends to be excessively lowered.
  • the alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.
  • the metal alkoxide has two or more alkoxy groups and the hydrocarbon group (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
  • 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 adhesive 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.
  • Silicone-containing release agent A release agent containing a plate-like carrier and a metal foil, silicone, and any one or more resins selected from an epoxy resin, a melamine resin, and a fluororesin
  • the adhesive strength suitable for temporary bonding can also be easily obtained by using and laminating the plate-like carrier and the metal foil.
  • Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, Examples thereof include brominated phenoxy resin.
  • the melamine-based resin examples include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol-modified melamine resin.
  • the melamine resin may be a mixed resin of the resin and a butylated urea resin, a butylated benzoguanamine resin, or the like.
  • the number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000.
  • the resin can be made into a paint, and the adhesive strength of the resin coating film formed by the silicone-containing release agent can be easily adjusted to a predetermined range.
  • examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.
  • silicone examples include methylphenyl polysiloxane, methyl hydropolysiloxane, dimethyl polysiloxane, modified dimethyl polysiloxane, and mixtures thereof.
  • the modification is, for example, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification.
  • the resin coating film if the film thickness is too small, the resin coating film is too thin and difficult to form, so that the productivity is likely to decrease. Moreover, even if a film thickness exceeds a fixed magnitude
  • the resin coating silicone functions as a release agent for the resin coating. Therefore, if the total amount of epoxy resin and melamine resin is too much compared to silicone, the adhesive strength imparted by the resin coating between the plate carrier and the metal foil increases, so that the peelability of the resin coating is increased. May decrease and may not be easily removed by hand. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-described adhesive strength is reduced, and therefore, the metal foil with a carrier may be peeled off during processing or processing. From this viewpoint, the total of the epoxy resin and the melamine resin is preferably contained in an amount of 10 to 1500 parts by weight, more preferably 20 to 800 parts by weight with respect to 100 parts by weight of silicone. Is preferred.
  • fluororesin functions as a release agent and has the effect of improving the heat resistance of the resin coating film. If the amount of fluororesin is too much compared to silicone, the aforementioned adhesive strength will be reduced, which may cause peeling during transportation or processing of the metal foil with carrier, and it will be uneconomical because the temperature required for the baking process described later will increase. It becomes. From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of silicone.
  • the resin coating film is selected from SiO 2 , MgO, Al 2 O 3 , BaSO 4 and Mg (OH) 2 in addition to silicone and epoxy resin and / or melamine resin and, if necessary, fluororesin 1 You may contain the surface roughening particle
  • the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the plate-like carrier or metal foil to which the resin coating film is applied becomes uneven and becomes a matte surface.
  • the content of the surface roughening particles is not particularly limited as long as the resin coating is roughened, but it is preferably 1 to 10 parts by mass with respect to 100 parts by mass of silicone.
  • the particle diameter of the surface roughened particles is preferably 15 nm to 4 ⁇ m.
  • the particle diameter means an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph or the like.
  • SEM scanning electron microscope
  • the amount of irregularities on the surface of the plate-like carrier or metal foil is about 4.0 ⁇ m in terms of the maximum height roughness Ry defined by JIS.
  • a temporary bonding method between the plate-like carrier and the metal foil when using the silicone-containing release agent will be described.
  • a temporary adhesion method using a silicone-containing release agent includes a step of applying a silicone-containing release agent to at least one surface of a plate-like carrier or a metal foil, and a baking step of curing the applied release agent. A step of hot pressing the metal foil and the plate-like carrier.
  • each step will be described.
  • the coating step is a step of forming a resin coating film by applying a silicone-containing release agent on one or both sides of the plate-like carrier.
  • the silicone-containing release agent can be obtained by dissolving an epoxy resin, a melamine resin, a fluororesin, and silicone in an organic solvent such as alcohol.
  • the blending amount (addition amount) in the resin coating is preferably 10 to 1500 parts by mass of the total of the epoxy resin and the melamine resin with respect to 100 parts by mass of the silicone.
  • the fluororesin is preferably 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
  • the coating method in the coating process is not particularly limited as long as a resin coating film can be formed, but a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, a method using an electrostatic coating machine, etc. are used. In view of the uniformity of the resin coating film and the ease of work, the gravure coating method is preferred.
  • the coating amount is preferably 1.0 to 2.0 g / m 2 so that the resin coating film 3 has a preferable film thickness: 0.5 to 5 ⁇ m.
  • the gravure coating method is a method in which a resin coating film is formed on the surface of a plate-like carrier by transferring a silicone-containing release agent filled in a recess (cell) provided on the roll surface to the plate-like carrier.
  • the lower part of the lower roll having the cell provided on the surface is immersed in a silicone-containing release agent, and the resin paint is pumped into the cell by the rotation of the lower roll.
  • the plate-like carrier is arranged between the lower roll and the upper roll arranged on the upper side of the lower roll, and the lower roll and the upper roll are held while pressing the plate-like carrier against the lower roll with the upper roll.
  • the plate-like carrier is conveyed, and the resin paint pumped into the cell is transferred (applied) to one side of the plate-like carrier.
  • a doctor blade on the side where the plate-shaped carrier is brought into contact with the surface of the lower roll, excess silicone-containing release agent pumped up on the roll surface other than the cell is removed, and the plate-like carrier is removed. A predetermined amount of a silicone-containing release agent is applied to the surface of the carrier.
  • a smoothing roll may be disposed on the carry-out side of the plate carrier to maintain the smoothness of the resin coating film.
  • the baking step is a step of subjecting the resin coating film formed in the coating step to a baking treatment at 125 to 320 ° C. (baking temperature) for 0.5 to 60 seconds (baking time).
  • the adhesive strength between the plate-like carrier provided by the resin coating film and the metal foil is in a predetermined range by subjecting the resin coating film formed of the resin coating of a predetermined blending amount to a baking process under predetermined conditions.
  • the baking temperature is the ultimate temperature of the plate carrier.
  • a conventionally well-known apparatus is used as a heating means used for a baking process.
  • the baking is insufficient, for example, when the baking temperature is less than 125 ° C. or when the baking time is less than 0.5 seconds, the resin coating becomes insufficiently cured, and the adhesive strength exceeds 200 gf / cm, The peelability is reduced.
  • baking is an excessive condition, for example, when baking temperature exceeds 320 degreeC, a resin coating film will deteriorate, the said adhesive strength will exceed 200 gf / cm, and workability
  • a plate-shaped carrier may change in quality by high temperature. Further, when the baking time exceeds 60 seconds, the productivity is deteriorated.
  • Silicone-containing mold release agents include silicone as a main agent, epoxy resin and melamine resin as curing agents, fluororesin as a release agent, SiO 2 , MgO, Al 2 O 3 , BaSO 4 and Mg (OH). It may consist of one or more kinds of surface roughened particles selected from 2 .
  • the silicone-containing release agent By further adding such surface-roughening particles to the silicone-containing release agent, the surface of the resin coating becomes uneven, and this unevenness makes the plate-like carrier or metal foil uneven, resulting in a matte surface.
  • the compounding quantity (addition quantity) of the surface roughening particle in a silicone containing mold release agent is 1 with respect to 100 mass parts of silicone. It is preferably ⁇ 10 parts by mass. Further, it is more preferable that the surface roughened particles have a particle size of 15 nm to 4 ⁇ m.
  • 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. If S is detected, the surface of the metal foil or resin has two or less mercapto groups in the molecule. It can be inferred that a compound is present, and if Al, Ti, Zr is detected, it can be inferred that the metal alkoxide is present on the surface of the metal foil or resin.
  • the method for producing a metal foil with a carrier according to the present invention is as described above. However, in carrying out the present invention, other processes may be performed between or before and after each process within a range that does not adversely affect each process. May be included. For example, you may perform the washing
  • 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 adhesive strength in the temporary adhesion region between the foil and the plate-like carrier is preferably 30 gf / cm or more, and more preferably 50 gf / cm or more.
  • the adhesive 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 adhesive strength after heating at 220 ° C. is described above in both 3 hours and 6 hours, or in 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 the adhesive strengths after 3 hours, 6 hours, and 9 hours satisfy the above-described range.
  • the adhesive strength between the metal foil and the plate-like carrier in the temporary adhesive region is measured in accordance with the 90-degree adhesive strength measuring method defined in JIS C6481, after removing the outer peripheral region by cutting.
  • the adhesive strength between the metal foil and the plate-like carrier in the adhesive region is 90 ° adhesive strength defined in JIS C6481 with respect to a cut piece including the adhesive region in the outer peripheral region after cutting the outer peripheral region. Measure according to the measurement method.
  • 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 adhesive strength after heating in an optimum range, for example, a glass transition temperature Tg of 120 to 320 ° C., preferably 170 to 240 ° C. .
  • the glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).
  • the thermal expansion coefficient of the resin is within + 10% and ⁇ 30% of the thermal expansion coefficient of the metal foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the metal foil and the resin, thereby reducing the occurrence of defective products and improving the yield.
  • the thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin, it will bend and will not flow through the printed wiring board manufacturing process. Therefore, it is usually 5 ⁇ m or more and 1000 ⁇ m or less, preferably 50 ⁇ m or more and 900 ⁇ m or less, and more preferably 100 ⁇ m or more and 400 ⁇ m or less.
  • the metal foil copper or copper alloy foil is a typical one, but foil of aluminum, nickel, zinc or the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used.
  • the metal foil generally has a thickness of 1 [mu] m or more, preferably 5 [mu] m or more, and 400 [mu] m or less, preferably 120 [mu] m or less, considering use as a wiring of a printed circuit board.
  • metal foils having the same thickness may be used, or metal foils having different thicknesses may be used.
  • the metal foil used may be subjected to various surface treatments.
  • metal plating for the purpose of imparting heat resistance Ni plating, Ni—Zn alloy plating, Cu—Ni alloy plating, Cu—Zn alloy plating, Zn plating, Cu—Ni—Zn alloy plating, Co—Ni alloy plating, etc.
  • Chromate treatment including the case where one or more alloy elements such as Zn, P, Ni, Mo, Zr, Ti, etc.
  • the chromate treatment liquid for imparting rust prevention and discoloration resistance, surface roughness (For example, copper electrodeposition grains, Cu—Ni—Co alloy plating, Cu—Ni—P alloy plating, Cu—Co alloy plating, Cu—Ni alloy plating, Cu—Co alloy plating, And copper alloy plating such as Cu—As alloy plating and Cu—As—W alloy plating).
  • the roughening treatment affects the adhesive strength between the metal foil and the plate carrier, and the chromate treatment also has a great influence.
  • Chromate treatment is important from the viewpoint of rust prevention and discoloration resistance, but significantly increases the adhesive strength, and is therefore meaningful as a means for forming an adhesive layer.
  • the adhesive strength between the resin and the metal foil is high.
  • the matte surface (M surface) of the electrolytic copper foil is used as the bonding surface with the resin, and surface treatment such as roughening treatment is performed. It is possible to improve the adhesive force by the chemical and physical anchor effect.
  • various binders can also be added on the resin side in order to increase the adhesive strength with the metal foil. By masking the temporary adhesion region with a photosensitive resin or the like, it is possible to selectively roughen the adhesion region.
  • the surface roughness of the bonded surface was measured in accordance with JIS B 0601: 2001 in order to adjust the adhesive strength between the metal foil and the plate-like carrier to the preferred range described above.
  • the ten-point average roughness (Rz jis) is preferably 3.5 ⁇ m or less, more preferably 3.0 ⁇ m or less.
  • reducing the surface roughness indefinitely takes time and increases costs, so it is preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more.
  • 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 adhesive strength such as roughening treatment may not be performed on the bonding surface of the metal foil with the plate-like carrier.
  • the binder for improving the adhesive force with metal foil is not added in the plate-shaped carrier in the temporary adhesion
  • this invention provides the use of the metal foil with a carrier mentioned above.
  • production of a multilayer laminated board including laminating a resin on at least one metal foil side of the metal foil with a carrier described above, and then repeating the resin or the metal foil one or more times, for example, 1 to 10 times. A method is provided.
  • a multilayer including a step of laminating a resin on the metal foil side of the metal foil with carrier described above, and then repeating the resin, single-sided or double-sided metal-clad laminate, or metal foil one or more times, for example, 1 to 10 times A method for manufacturing a laminate is provided.
  • the carrier-attached metal foil may be cut in the thickness direction at a portion inside the portion where the carrier and the metal foil are bonded via an adhesive layer. it can.
  • the cutting step is preferably performed after the completion of the lamination of the multilayer metal-clad laminate in order to sufficiently exhibit the effects of the present invention, but can also be performed before or during the lamination.
  • the cutting process is performed during or after the completion of lamination, not only the metal foil with carrier but also the laminated resin and substrate are usually cut together.
  • a step of removing a part or all of the metal foil exposed by the peeling by etching may be performed as necessary.
  • 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 full additive method and a semi-additive method.
  • 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.
  • 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.
  • the resin is laminated on the metal foil side of the metal foil with carrier described above, and then the resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, or metal foil is repeatedly laminated at least once, for example, 1 to 10 times.
  • a method for manufacturing a build-up substrate including the step of:
  • a hole is made in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, or a resin.
  • the method 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 further includes the step of bringing the metal foil into close contact with one surface on the surface on which the wiring is formed, and further laminating the carrier side of another metal foil with a carrier according to the present invention. You can also. 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 metal foil with a carrier can be cut in the thickness direction at a portion inside the portion where the carrier and the metal foil are bonded via an adhesive layer.
  • the cutting step is preferably performed after completion of the lamination of the build-up substrate in order to sufficiently exhibit the effects of the present invention, but can also be performed before or during the lamination.
  • the cutting process is performed during or after the completion of lamination, not only the metal foil with carrier but also the laminated resin and substrate are usually cut together.
  • the cutting location should be outside the wiring formation region so that the wiring formation is not hindered or the already formed wiring is not cut.
  • a step of peeling and separating the plate-like carrier and the metal foil and further removing a part or all of the exposed metal foil by etching may be further performed. it can.
  • 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 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 by the method according to the present invention.
  • the metal foil with carrier 11 in which the metal foil 11a is adhered to one surface of the plate-like carrier 11c by the method according to the present invention.
  • a desired number of prepregs 12, then a two-layer metal-clad laminate called an inner core 13, then a prepreg 12, and then a metal foil 11 with a carrier are sequentially stacked to form a set of four layers.
  • a metal-clad laminate assembly unit is completed.
  • the unit 14 (referred to as “page”) is repeated about 10 times to form a press assembly 15 (referred to as “book”).
  • a large number of four-layer metal-clad laminates can be produced simultaneously by sandwiching the book 15 between the laminated molds 10 and setting the book 15 in a hot press machine, followed by pressure 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.
  • a metal-clad laminate having four or more layers can generally be produced in the same process by increasing the number of inner core layers.
  • a resin as an insulating layer, a two-layer circuit board, and a resin as an insulating layer are sequentially stacked, and the metal foil side is in contact with the resin on the metal foil side of the present invention.
  • a build-up substrate can be manufactured by sequentially stacking metal foils of the metal foil with a carrier to form a laminate.
  • 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 is removed after plating.
  • wiring is formed by removing unnecessary portions of the metal foil and the electroless plating portion and the electrolytic plating portion by etching. In this way, a build-up substrate can be manufactured.
  • the process from the lamination of the resin and the copper foil to the wiring formation may be repeated a plurality of times to form a multilayer build-up board.
  • the metal side of the metal foil with a carrier having the metal foil adhered to one side of the present invention may be contacted and laminated, or once the resin is laminated Alternatively, one metal foil of the metal foil with 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 used for manufacturing the build-up substrate.
  • a resin for example, an insulating layer
  • Prepreg or photosensitive resin is laminated.
  • 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. When a plating resist is used, the plating resist is removed after plating. Next, wiring is formed by removing unnecessary portions of the electroless plating portion or the electrolytic plating portion by etching. In this way, a build-up substrate can be manufactured.
  • the steps from resin lamination to wiring formation may be repeated a plurality of times to form a multilayered build-up substrate. Furthermore, on the outermost surface of this build-up substrate, the metal side of the metal foil with a carrier having the metal foil adhered to one side of the present invention may be contacted and laminated, or once the resin is laminated Alternatively, one metal foil of the metal foil with 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 build-up wiring board is formed by forming wiring on the surface through a plating process and / or etching process, and further peeling the carrier from the metal foil with carrier. Is completed. You may form wiring by removing a part of metal foil with respect to the peeling surface of the metal foil exposed after peeling isolation
  • a plurality of electrolytic copper foils (550 mm ⁇ 550 mm ⁇ thickness 12 ⁇ m) were prepared, and nickel-zinc (Ni—Zn) alloy plating treatment and chromate were performed on the shiny (S) surface of each electrolytic copper foil under the following conditions.
  • (Cr—Zn chromate) treatment was performed, and then silane coupling treatment was performed according to the experimental example number.
  • a release agent is applied to the S surface or the prepreg surface, and a prepreg (FR-4 resin, 550 mm ⁇ 550 mm ⁇ thickness 200 ⁇ m) manufactured by Nanya Plastic Co., Ltd. is used as the resin with the S surface of the electrolytic copper foil. Bonding and hot pressing at 170 ° C. for 100 minutes were performed to prepare a copper foil with a carrier.
  • Nickel-zinc alloy plating Ni concentration 17g / L (added as NiSO 4 ) Zn concentration 4g / L (added as ZnSO 4 ) pH 3.1 Liquid temperature 40 °C Current density 0.1-10A / dm 2 Plating time 0.1 to 10 seconds
  • an aqueous solution of the mold release agent is applied using a spray coater, and then the copper foil surface is dried in air at 100 ° C. and then attached to the prepreg. Combined.
  • the use conditions of the release agent the type of release agent, the stirring time from when the release agent is dissolved in water to before application, the concentration of the release agent in the aqueous solution, the alcohol concentration in the aqueous solution, the pH of the aqueous solution Is shown in Table 1.
  • the formation of a resin coating using a silicone-containing release agent on the S-surface or prepreg is performed by applying a composition for a resin coating having the composition shown in Table 1 by a gravure coating method, and then a doctor blade. The thickness was adjusted to 2-4 ⁇ m using Moreover, the applied resin coating film was baked by heating at 150 ° C. for 30 seconds.
  • bisphenol A type epoxy resin was used as the epoxy resin shown in Table 1
  • methyl etherified melamine resin was used as the melamine resin.
  • the outer periphery of the copper foil and the prepreg, which do not require a release agent treatment, was appropriately masked according to the experimental example, and after completion of the release agent treatment, the masking was removed to obtain an adhesive region.
  • Table 1 shows the types of copper foil bonding surfaces, surface treatment conditions and surface roughness Rz jis, release agent usage conditions, prepreg types, and lamination conditions of copper foil and prepreg. .
  • the copper foil with a carrier was subjected to each heat treatment under the conditions shown in Table 1 assuming that a thermal history is applied to the copper foil with a carrier during further heat treatment such as circuit formation.
  • the copper foil with carrier is immersed in a commercially available desmear solution and the maximum value of the erosion width of the metal foil and the carrier interface is visually confirmed. did.
  • desmear liquid DS224 manufactured by Nihon McDermid Co., Ltd. was used and treated at a liquid temperature of 75 ° C. for 25 minutes. The results are shown in Table 3.
  • the adhesive strength of the outer peripheral region (adhesive layer) of the metal foil with a carrier produced under the above conditions was measured according to the 90-degree adhesive strength measurement method specified in JIS C6481. If the adhesive area is too narrow to measure the adhesive strength, the measurement is performed by appropriately adjusting the circuit width for measuring the adhesive strength according to the above-described method, and the adhesive strength is 90 degrees adhesive strength (gf / cm) at 10 mm width. Converted. Assuming that a thermal history is applied to the metal foil with a carrier during further heat treatment such as circuit formation, the adhesive strength after heat treatment under the conditions shown in Table 3 was also measured. The results are shown in Table 3.
  • the treatment region (temporary adhesion region) of the release agent in each experimental example, the treatment method of the adhesion region in the outer peripheral portion, and the adhesive strength of this portion will be described in detail.
  • ⁇ Experimental examples 1, 4 to 6> The treatment area of the release agent was set as shown in FIG.
  • the width of the adhesive region at both ends of the copper foil was 3 mm in Experimental Example 1, 1 mm in Experimental Example 4, 20 mm in Experimental Example 5, and 50 mm in Experimental Example 6. It is the aforementioned chromate layer formed on the copper foil that functions as an adhesive layer in the adhesive region.
  • the adhesive strength of this adhesive region was 360 gf / cm, and it had sufficient adhesive strength (corresponding to Experimental Example 12 where no release agent was treated).
  • Example 2 7 to 10 The treatment area (temporary adhesion area) of the release agent was as shown in FIG.
  • the width of the adhesion region of the copper foil and the prepreg outer peripheral part was 3 mm in Experimental Example 2, 1 mm in Experimental Example 7, 20 mm in Experimental Example 8, and 50 mm in Experimental Examples 9 and 10.
  • the chromate layer formed on the copper foil functions as the adhesive layer in the adhesion region.
  • silane coupling agent used in the adhesive layer examples include 3-glycidoxypropyltrimethoxysilane in Experimental Example 7, N-2-aminoethyl-3-aminopropyltrimethoxysilane in Experimental Example 8, and vinyl trimethyl in Experimental Example 9.
  • About all the silane coupling agents, what was stirred at room temperature for 12 hours at pH 7.0 using a 2.0 volume% aqueous solution was applied using a roll coater, and then dried in air at 100 ° C. for 5 minutes.
  • the adhesive strengths of the strong adhesion portions in Experimental Examples 7 to 10 are 330 to 550 gf / cm, which is sufficient.
  • the strong bonding portion has a bonding strength of 360 gf / cm and has a sufficient bonding strength.
  • the adhesive strength tends to decrease.
  • a carrier-attached copper foil was produced under the same conditions as in Experimental Example 2, except that the release agent was treated on the entire surface of the copper foil. That is, the adhesive strength of the outer peripheral portion is the same as that of the central portion.
  • the amount of the chemical solution soaked was as large as 20 mm or more in all the copper foil with carrier and after the heat treatment thereof, and it was found that the soaking of the chemical solution at the interface between the copper foil and the prepreg could not be prevented.
  • the release agent can be processed on the surface of the copper foil or the surface of the plate-like carrier (prepreg), and then the adhesive strength of the laminate, the adhesive strength after heating, and the peeling It can be seen that the same results were obtained in workability.
  • 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.
  • a 100 ⁇ m diameter hole penetrating the copper foil on both surfaces of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine.
  • the copper foil surface on the copper foil with a 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 are electrolessly plated with copper and electroplated in order.
  • Plating was performed to form an electrical connection between the copper foil on the carrier-attached copper foil 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 manner, a four-layer buildup substrate can be produced.
  • Two sets of two-layer build-up wiring boards were obtained by mechanically peeling and separating the plate-like carrier and the copper foil.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

La présente invention concerne une feuille métallique fixée à un support qui permet d'ajuster la résistance à l'arrachement entre une résine, un support de type plaque et une feuille métallique, et qui permet également d'éviter la séparation du support de la feuille métallique au cours du transport et du traitement (c'est-à-dire au cours de la manipulation). Selon l'invention, la feuille métallique fixée à un support (230) comprend : une résine, un support de type plaque (240) ; et une feuille métallique (200) empilée sur au moins une surface du support (240). Dans les interfaces entre le support (240) et la feuille métallique (200) : le support et la feuille métallique sont liés avec une résistance à l'arrachement comprise dans la plage de 201 à 1 000 gf/cm par le biais d'une couche de liaison (220) disposée au moins au niveau des angles d'une région périphérique extérieure ; et un agent anti-adhérent est utilisé au niveau d'une région restante (210) de sorte que le support (240) et la feuille métallique (200) sont liés temporairement avec une résistance à l'arrachement comprise dans la plage de 10 à 200 gf/cm.
PCT/JP2013/077183 2012-10-04 2013-10-04 Feuille métallique fixée à un support WO2014054812A1 (fr)

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JP2017177651A (ja) * 2016-03-31 2017-10-05 東レＫｐフィルム株式会社 離型フィルム付銅箔
WO2018003703A1 (fr) * 2016-07-01 2018-01-04 三菱瓦斯化学株式会社 Procédé de fabrication d'un substrat de boîtier permettant de porter un élément semi-conducteur, et procédé de fabrication d'un substrat monté sur un élément semi-conducteur
CN108696988A (zh) * 2017-03-31 2018-10-23 Ｊｘ金属株式会社 附脱模层铜箔、积层体、印刷配线板的制造方法及电子机器的制造方法
KR20200079515A (ko) 2018-02-20 2020-07-03 미쓰이금속광업주식회사 유리 캐리어를 구비하는 구리박 및 그 제조 방법
WO2022124116A1 (fr) 2020-12-08 2022-06-16 三井金属鉱業株式会社 Feuille métallique fixée à un support et son procédé de production

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US10863621B2 (en) 2014-06-03 2020-12-08 Mitsui Mining & Smelting Co., Ltd. Metal foil with releasing resin layer, and printed wiring board
JP5936794B2 (ja) * 2014-06-03 2016-06-22 三井金属鉱業株式会社 剥離樹脂層付金属箔及びプリント配線板
CN106232350A (zh) * 2014-06-03 2016-12-14 三井金属矿业株式会社 带剥离树脂层的金属箔和印刷电路板
WO2015186589A1 (fr) * 2014-06-03 2015-12-10 三井金属鉱業株式会社 Feuille métallique pourvue de couche de résine antiadhésive, et carte de câblage imprimée
US20170151755A1 (en) * 2015-12-01 2017-06-01 Materion Corporation Metal-on-ceramic substrates
US11046051B2 (en) * 2015-12-01 2021-06-29 Materion Corporation Metal-on-ceramic substrates
JP2017177651A (ja) * 2016-03-31 2017-10-05 東レＫｐフィルム株式会社 離型フィルム付銅箔
JPWO2018003703A1 (ja) * 2016-07-01 2019-05-16 三菱瓦斯化学株式会社 半導体素子搭載用パッケージ基板の製造方法及び半導体素子実装基板の製造方法
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TWI718316B (zh) * 2016-07-01 2021-02-11 日商三菱瓦斯化學股份有限公司 半導體元件搭載用封裝基板之製造方法及半導體元件安裝基板之製造方法
WO2018003703A1 (fr) * 2016-07-01 2018-01-04 三菱瓦斯化学株式会社 Procédé de fabrication d'un substrat de boîtier permettant de porter un élément semi-conducteur, et procédé de fabrication d'un substrat monté sur un élément semi-conducteur
JP7044997B2 (ja) 2016-07-01 2022-03-31 三菱瓦斯化学株式会社 半導体素子搭載用パッケージ基板の製造方法及び半導体素子実装基板の製造方法
CN108696988A (zh) * 2017-03-31 2018-10-23 Ｊｘ金属株式会社 附脱模层铜箔、积层体、印刷配线板的制造方法及电子机器的制造方法
KR20200079515A (ko) 2018-02-20 2020-07-03 미쓰이금속광업주식회사 유리 캐리어를 구비하는 구리박 및 그 제조 방법
US11756845B2 (en) 2018-02-20 2023-09-12 Mitsui Mining & Smelting Co., Ltd. Copper foil with glass carrier and production method therefor
WO2022124116A1 (fr) 2020-12-08 2022-06-16 三井金属鉱業株式会社 Feuille métallique fixée à un support et son procédé de production
KR20230117139A (ko) 2020-12-08 2023-08-07 미쓰이금속광업주식회사 캐리어를 구비하는 금속박 및 그 제조 방법

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TW201422424A (zh) 2014-06-16

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