WO2023063357A1 - 絶縁層を含む多層構造体 - Google Patents

絶縁層を含む多層構造体 Download PDF

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Publication number
WO2023063357A1
WO2023063357A1 PCT/JP2022/038065 JP2022038065W WO2023063357A1 WO 2023063357 A1 WO2023063357 A1 WO 2023063357A1 JP 2022038065 W JP2022038065 W JP 2022038065W WO 2023063357 A1 WO2023063357 A1 WO 2023063357A1
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Prior art keywords
copper foil
multilayer structure
mass
aromatic
insulating layer
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Ceased
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PCT/JP2022/038065
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English (en)
French (fr)
Japanese (ja)
Inventor
亨 荒井
諒介 菅藤
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Denka Co Ltd
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Denka Co Ltd
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Filing date
Publication date
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to CN202411678747.2A priority Critical patent/CN119239086A/zh
Priority to US18/701,376 priority patent/US20250010581A1/en
Priority to JP2023530919A priority patent/JP7445092B2/ja
Priority to KR1020247009283A priority patent/KR20240051988A/ko
Priority to EP22881052.9A priority patent/EP4417413A4/en
Priority to CN202280057657.4A priority patent/CN117858798B/zh
Publication of WO2023063357A1 publication Critical patent/WO2023063357A1/ja
Priority to JP2024025889A priority patent/JP7638410B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic 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
    • B32B15/04—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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P3/00—Waveguides; Transmission lines of the waveguide type
    • H01P3/02—Waveguides; Transmission lines of the waveguide type with two longitudinal conductors
    • H01P3/08—Microstrips; Strip lines
    • H01P3/081—Microstriplines

Definitions

  • the present invention relates to a multilayer structure having a copper foil smooth surface and an insulating layer made of a composition having high adhesiveness.
  • Patent Document 3 discloses an ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer obtained from a specific coordination polymerization catalyst and having a specific composition and blending, and a cured product consisting of a non-polar vinyl compound copolymer. body is shown.
  • ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer obtained from a specific coordination polymerization catalyst and having a specific composition and blending, and a cured product consisting of a non-polar vinyl compound copolymer. body is shown.
  • the aromatic polyene divininylbenzene
  • a hydrocarbon-based copolymer macromonomer can be obtained.
  • a cured product obtained from a similar composition of an olefin-aromatic vinyl compound-aromatic polyene copolymer and auxiliary raw materials is characterized by a low dielectric constant and a low dielectric loss tangent.
  • auxiliary raw materials Depending on the selection, it is possible to provide a wide range of physical properties from soft to hard (Patent Documents 4 and 5). Also, these materials can exhibit high adhesion (adhesion strength) to the roughened copper foil surface as shown in the examples. Therefore, it is considered suitable for various substrate materials and insulating materials for high-frequency signals.
  • the insulating material is in contact with the smooth surface of the copper foil.
  • High adhesive strength peel strength
  • sheet-shaped or film-shaped interlayer insulating materials are in contact with the smooth surface of the copper foil at least partially or at least on one side, and are required to have high adhesive strength with this.
  • the disclosed patent documents do not disclose a technique for imparting high adhesiveness (adhesive strength) to the smooth surface of the copper foil to the insulating material.
  • the present application can provide the following modes for solving the above problems.
  • Aspect 1 one or more insulating layers; one or more resin layers; A multilayer structure comprising one or more copper foils having a smooth surface and a roughened surface,
  • the insulating layer contains an olefin-aromatic vinyl compound-aromatic polyene copolymer and a surface modifier,
  • the resin layer is selected from the group consisting of polyimide (PI), liquid crystal polymer (LCP), polyphenylene ether (PPE), polyfunctional aromatic vinyl resin (ODV), epoxy resin, and the same composition as the insulating layer.
  • At least one surface of each of the insulating layers is adhered to the smooth surface of the copper foil,
  • At least one surface of the resin layer adheres to the roughened surface of the copper foil and the resin layer does not adhere to the smooth surface of the copper foil, or the resin layer has A multilayer structure characterized in that both sides are not adhered to said copper foil.
  • At least one surface of the insulating layer has a recessed portion in the lamination direction, and the copper foil is adhered so that it fits in the recessed portion, so that a part of the surface is the smoothness of the copper foil.
  • Aspect 4 The multilayer structure according to any one of aspects 1 to 3, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies all of the following conditions (1) to (4).
  • the copolymer has a number average molecular weight of 500 or more and less than 100,000.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0 to 70% by mass or 0 to 98% by mass. is.
  • the aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms having a plurality of vinyl groups and/or vinylene groups in the molecule, and vinyl groups and/or derived from aromatic polyene units;
  • the content of vinylene groups is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 to 20 carbon atoms, the content of olefin monomer units is 10% by mass or more, and the olefin monomer units and aromatic vinyl compound monomers The total amount of body units and aromatic polyene monomer units is 100% by mass.
  • Aspect 5 The multilayer structure according to any one of aspects 1 to 4, wherein the insulating layer further includes one or more selected from (a) to (c) below. (a) curing agent (b) one or more resins selected from hydrocarbon elastomers, polyphenylene ether resins and aromatic polyene resins (c) polar monomers
  • Aspect 6 Aspects 1 to 5, wherein the content of the surface modifier in the insulating layer is 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer. 3. The multilayer structure according to claim 1.
  • a cured multilayer structure obtained by curing the multilayer structure according to any one of aspects 1 to 6.
  • a radio frequency transmission line, multilayer CCL substrate, multilayer FCCL substrate, antenna, or coverlay comprising the cured multilayer structure of aspect 7.
  • an insulating layer exhibiting low dielectric constant, dielectric loss tangent, low water absorption, and high insulation is adhered to a copper foil smooth surface with high adhesive strength (peel strength), making it useful as a high-frequency multilayer substrate.
  • a multilayer structure can be provided.
  • FIG. 1 shows the structure of a basic unit that may be included in part or all of a multilayer structure according to the present invention; Specific examples of structures that may be included in part or all of the multilayer structure according to the present invention are shown. Specific examples of structures that may be included in part or all of the multilayer structure according to the present invention are shown. A modified example of the above basic unit is shown.
  • the basic unit of the multilayer structure is a structure (shown in FIG. 1) including a copper foil, a resin layer adhered to the roughened surface of the copper foil, and an insulating layer adhered to the smooth surface of the copper foil. .
  • the multilayer structure may contain one or more of the basic units, and may contain a combination of the basic units and another layer.
  • the insulating layer (one or more layers) included in the present multilayer structure is a concept including an interlayer insulating material and a coverlay.
  • the interlayer insulating material is a concept that includes the concept of an interlayer adhesive material and a bonding sheet.
  • the sheet also includes the concept of film. Further, even if the term "film” is used in this specification, the concept of "sheet” is also included.
  • compositions according to the invention are described in more detail below.
  • composition as used herein is a concept that includes varnish. That is, among the compositions, those that are particularly liquid are described as varnishes.
  • the copper foil (one or more sheets) included in the present multilayer structure may be any copper foil that can be used for wiring and substrates. Although the thickness is not particularly limited, it generally ranges from 1 to 500 ⁇ m, preferably from 5 to 50 ⁇ m.
  • a copper foil suitable for high frequencies is preferable, and may be a rolled copper foil or an electrolytic copper foil.
  • the present copper foil has a roughened surface (also known as matte surface, sometimes referred to as M surface) and a smooth surface (glossy surface or shine surface, sometimes referred to as S surface).
  • the roughened surface of the copper foil may be a copper foil having a surface roughness (maximum height) Rz defined in JIS B0601:2001 of preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less.
  • the roughened surface of the copper foil may be a copper foil having a surface roughness (maximum height) Rz defined in JIS B0601:2001 preferably exceeding 0.5 ⁇ m.
  • Such copper foil can be obtained from Furukawa Electric Co., Ltd., JX Metals Co., Ltd., Mitsui Kinzoku Mining Co., Ltd., and the like.
  • the smooth surface of the copper foil is a surface that is not a roughened surface and which is relatively smooth compared to the roughened surface, which copper foil used for wiring and substrates has.
  • the smooth surface generally has a surface roughness (maximum height) Rz of 0.5 ⁇ m or less as defined in JIS B0601:2001, but as described above, it is a relatively smooth surface compared to the roughened surface. , or because it is a surface having relatively high gloss, there is no particular limitation.
  • Those skilled in the art can readily recognize and distinguish between smooth and roughened surfaces of copper foil. Since the roughened surface of the copper foil is used for bonding with the base film or the substrate, the interlayer insulating material of the multilayer substrate is required to have high adhesiveness to the remaining smooth surface.
  • the (one or more) resin layers included in the multilayer structure are polyimide (PI), liquid crystal polymer (LCP), polyphenylene ether (PPE), polyfunctional aromatic vinyl resin (ODV), epoxy resin, or the insulating layer described above. It is a resin layer selected from the same resin (composition) as that of the It is distinguished from the insulating layer by not adhering to a smooth surface or not adhering to a copper foil at all.
  • the case where the present resin layer has the same composition as the insulating layer means that the present resin layer "contains an olefin-aromatic vinyl compound-aromatic polyene copolymer and a surface modifier" like the insulating layer.
  • the thickness of the resin layer is arbitrary, and preferably 10 ⁇ m to 1 mm.
  • the resin layer preferably contains a reinforcing material such as a filler or glass cloth.
  • One surface of the resin layer may be adhered in advance to the roughened surface of the copper foil.
  • the polyimide (PI) is a concept including modified polyimide (MPI) having a reduced dielectric constant, dielectric loss tangent, and water absorption.
  • a curable PPE having a functional group is preferable as the above polyphenylene ether.
  • part or all of the multilayer structure has the basic unit shown in FIG. 1 or a repeating structure thereof, and may further have the insulating layer, the resin layer, or the copper foil. . As a specific example, it may consist of one or a combination of structures (1) to (5) shown in FIGS.
  • some or all of the above basic units may be replaced with variations of the basic units shown in FIG.
  • some or all of the above structures (1) to (5) may be replaced with modified examples of the basic units shown in FIG. That is, at least one surface of the insulating layer has a recessed portion in the lamination direction, and the copper foil is adhered so that it fits in the recessed portion, so that part of the surface is the copper foil. It means that it may have a configuration in which it is adhered to a smooth surface and another part of the surface is adhered to the resin layer. That is, in this way, a structure in which the resin layer is partially directly adhered to the insulating layer may be adopted.
  • Such replacement can be performed, for example, by partially removing the copper foil by etching and replacing that portion with an insulating layer.
  • the area of each layer included in the multilayer structure may not be constant, and may be, for example, divided into islands or provided with recesses.
  • one or more of the layers having the present multilayer structure may have through holes or via holes (through hole vias, interstitial vias, blind vias, buried vias, etc.), but in this specification , these holes are considered to be excluded from the definition of the layer structure of the present multilayer structure (the presence of holes is omitted in the above drawings).
  • the thickness of the insulating layer included in the multilayer structure is arbitrary, but generally 1 ⁇ m to 500 ⁇ m, preferably 5 ⁇ m to 100 ⁇ m.
  • the composition forming the insulating layer contained in the multilayer structure contains an olefin-aromatic vinyl compound-aromatic polyene copolymer as its main component, and further comprises the olefin-aromatic vinyl compound-aromatic polyene copolymer 100. It is preferable to include 0.01 to 5 parts by mass of a surface modifier, preferably a silane coupling agent, based on the parts by mass. At least a portion of the insulating layer is in contact with the smooth surface of the copper foil.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer may be contained in an amount of 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, relative to the entire composition.
  • the present olefin-aromatic vinyl compound-aromatic polyene copolymer can be obtained by copolymerizing each monomer of an olefin, an aromatic vinyl compound and an aromatic polyene.
  • the olefin monomer is one or more selected from ⁇ -olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms, substantially free of oxygen, nitrogen, and halogen, and composed of carbon and hydrogen.
  • ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decane, 1-dodecane, 4-methyl-1-pentene, 3,5,5 -trimethyl-1-hexene can be exemplified.
  • Examples of cyclic olefins having 5 to 20 carbon atoms include norbornene and cyclopentene.
  • the olefin that can be preferably used is a combination of ethylene with an ⁇ -olefin other than ethylene or a cyclic olefin, or ethylene alone.
  • the mass ratio of ethylene alone or the ⁇ -olefin component other than ethylene contained/the ethylene component is preferably 1/7 or less, more preferably 1/10 or less, the resulting cured product adheres to copper foil or copper wiring It is preferable because the strength can be increased. More preferably, the content of ⁇ -olefin monomer components other than ethylene contained in the copolymer is 6% by mass or less, most preferably 4% by mass or less, or the olefin is ethylene alone.
  • the glass transition temperature of the finally cured ethylene- ⁇ -olefin-aromatic vinyl compound-aromatic polyene copolymer depends on the type and content of the ⁇ -olefin. , can be freely adjusted in the range of -60°C to -10°C.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and examples thereof include styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes.
  • the aromatic polyene monomer is a polyene having a carbon number of 5 or more and 20 or less having a plurality of vinyl groups and/or vinylene groups in the molecule, preferably ortho-, meta-, or para-divinylbenzene or a mixture thereof.
  • divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, p-3-butenylstyrene, etc. have an aromatic vinyl structure, contain substantially no oxygen, nitrogen, or halogen, and are composed of carbon and hydrogen. is a compound.
  • Bifunctional aromatic vinyl compounds such as 1,2-bis(vinylphenyl)ethane (abbreviation: BVPE) described in JP-A-2004-087639 can also be used.
  • BVPE 1,2-bis(vinylphenyl)ethane
  • ortho-, meta-, and para-divinylbenzenes, or mixtures thereof, are preferably used, and most preferably, mixtures of meta- and para-divinylbenzenes.
  • these divinylbenzenes are referred to as divinylbenzenes.
  • divinylbenzenes When divinylbenzenes are used as the aromatic polyene, they are preferable because they have high curing efficiency and are easy to cure.
  • the above olefins, aromatic vinyl compounds, and aromatic polyene monomers may also include olefins containing polar groups such as oxygen atoms, nitrogen atoms, etc., aromatic vinyl compounds containing oxygen atoms, nitrogen atoms, etc., or , It may contain an aromatic polyene containing oxygen atoms, nitrogen atoms, etc., but the total mass of the monomers containing these polar groups is preferably 10% by mass or less, and 3% by mass of the total mass of the composition. The following are more preferable, and it is most preferable not to contain a monomer containing a polar group. By setting the content to 10% by mass or less, the dielectric properties (low dielectric constant/low dielectric loss) of the cured product obtained by curing the present composition can be improved.
  • the present olefin-aromatic vinyl compound-aromatic polyene copolymer preferably satisfies one or more of the following conditions (1) to (4), and more preferably satisfies all of them.
  • the copolymer has a number average molecular weight of 500 or more and less than 100,000.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0 to 98% by mass, preferably 0 to 70% by mass. % or less.
  • the aromatic polyene is one or more selected from polyenes having 5 to 20 carbon atoms having a plurality of vinyl groups and/or vinylene groups in the molecule, and vinyl groups and/or derived from aromatic polyene units;
  • the content of vinylene groups is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 to 20 carbon atoms, the content of olefin monomer units is 10% by mass or more, and the olefin monomer units and aromatic vinyl compound monomers The total amount of body units and aromatic polyene monomer units is 100% by mass.
  • the copolymer may have a number average molecular weight (Mn) of 500 or more and less than 100,000.
  • Mn number average molecular weight
  • the number average molecular weight of 500 or more and less than 100,000 means that the molecular weight in terms of standard polystyrene obtained by the GPC (gel permeation chromatography) method falls within that range. That is.
  • the content of the aromatic vinyl compound monomer units contained in the present copolymer may be 0% by mass or more and 98% by mass or less, more preferably 0% by mass or more and 70% by mass or less, and most preferably 10% by mass or more. It is 60% by mass or less.
  • the content of the aromatic vinyl compound monomer units is 70% by mass or less, the glass transition temperature of the cured body of the finally obtained composition is lower than around room temperature, and the toughness and elongation at low temperatures are improved. It is preferable because it can be done.
  • the content of the aromatic vinyl compound monomer unit is 10% by mass or more, the aromaticity of the present copolymer is improved, compatibility with the flame retardant and filler is improved, and bleeding out of the flame retardant can be avoided.
  • the effect that the filling property of the filler can be improved can be obtained. Further, when the content of the aromatic vinyl compound monomer unit is 10% by mass or more, it is possible to obtain a cured product of the composition having high adhesion strength to copper foil or copper wiring.
  • the content of vinyl groups and/or vinylene groups derived from aromatic polyene units may be 1.5 or more and less than 20 per number average molecular weight, The number is preferably 2 or more and less than 20, and most preferably 3 or more and less than 20.
  • the vinyl group content derived from the aromatic polyene unit (divinylbenzene unit) per number average molecular weight in the copolymer is determined by the GPC (gel permeation chromatography) method known to those skilled in the art.
  • the vinyl group content derived from the aromatic polyene unit obtained by 1 H-NMR measurement is 0.45% by mass, and GPC
  • the standard polystyrene equivalent number average molecular weight by measurement is 36000
  • the molecular weight of the vinyl group derived from the aromatic polyene unit in the number average molecular weight is the product of these, 162, which is divided by the formula weight of the vinyl group 27. So, it becomes 6.0.
  • the vinyl group content derived from the aromatic polyene unit per number average molecular weight in the present copolymer is required to be 6.0.
  • the assignment of peaks obtained in 1 H-NMR measurements of copolymers is known from the literature.
  • a method for determining the composition of a copolymer from comparison of peak areas obtained by 1 H-NMR measurement is also known.
  • it is also possible to improve the accuracy of the composition by adding the data of the peak areas and their ratios of the 13 C-NMR spectrum measured in a known quantitative mode to the present 1 H-NMR measurement method.
  • the content of divinylbenzene units in the copolymer is determined from the peak intensity of the vinyl group derived from the divinylbenzene units (by 1 H-NMR measurement). That is, from the content of vinyl groups derived from divinylbenzene units, the content of divinylbenzene units is determined on the assumption that one vinyl group is derived from one divinylbenzene unit in the copolymer.
  • the content of olefin monomer units is preferably 10% by mass or more, more preferably 20% by mass or more, and most preferably 30% by mass or more.
  • the total amount of the olefin monomer units, the aromatic vinyl compound monomer units and the aromatic polyene monomer units is 100% by mass.
  • the content of the olefin monomer unit is 10% by mass or more, the toughness (elongation) and impact resistance of the finally obtained cured body are improved, and cracks during curing and during the heat cycle test of the cured body cracks are less likely to occur.
  • the content of olefinic monomer units is preferably 90% by mass or less.
  • the present copolymer may be a mixture of multiple types of copolymers.
  • the olefin-aromatic polyene copolymer containing no aromatic vinyl compound monomer unit specifically includes an ethylene-divinylbenzene copolymer, an ethylene-propylene-divinylbenzene copolymer, Preferred examples include ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, and ethylene-1-octene-divinylbenzene copolymer.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer containing aromatic vinyl compound monomer units includes ethylene-styrene-divinylbenzene copolymer, ethylene-propylene-styrene-divinyl Examples include benzene copolymers, ethylene-1-hexene-styrene-divinylbenzene copolymers, and ethylene-1-octene-styrene-divinylbenzene copolymers.
  • the composition of the present invention contains a surface modifying agent for the purpose of improving adhesion to a copper foil for wiring.
  • the purpose is to increase the adhesion strength (peel strength) to the smooth surface of the copper foil.
  • the amount (content) of the surface modifier used with respect to 100 parts by mass of the olefin-aromatic vinyl compound-aromatic polyene copolymer is preferably 0.001 to 10 parts by mass, and is preferably in the range of 0.01 to 5 parts by mass. More preferably, the range of 0.01 to 1 part by mass is most preferable.
  • the amount of the surface modifier used is 10 parts by mass or less, the dielectric constant and dielectric loss tangent of the cured product obtained from the composition are low, which satisfies the object of the present invention.
  • a known surface modifier can be used in the present invention.
  • examples of such surface modifiers include silane-based surface modifiers (also known as silane coupling agents), titanate-based surface modifiers, and isocyanate-based surface modifiers.
  • silane-based surface modifiers are used.
  • One or more of these surface modifiers may be used.
  • Such silane-based surface modifiers are available from Shin-Etsu Chemical Co., Ltd., Dow Corning, and Evonik.
  • a silane-based surface modifier is a silane compound having a functional group and a hydrolytically condensable group in its molecule.
  • Examples of functional groups include vinyl groups such as vinyl, methacryloxy, acryloxy, and styryl, amino groups, epoxy groups, mercapto groups, sulfide groups, isocyanate groups, and halogens.
  • the functional group is preferably one or more selected from vinyl group, amino group, epoxy group, methacryloxy group, and acryloxy group, and most preferably one or more selected from amino group, methacryloxy group, and epoxy group. preferable.
  • One or more of these functional groups may be present in the molecule.
  • One or more of these surface modifiers can be used.
  • Examples of the silane-based surface modifier having a vinyl group as a functional group include vinyltrimethoxysilane and vinyltriethoxysilane.
  • silane coupling agents having a styryl group as a functional group examples include p-styryltrimethoxysilane.
  • a silane coupling agent having an acryloxy group as a functional group can be exemplified by 3-acryloxypropyltrimethoxysilane.
  • Silane coupling agents having a methacryloxy group as a functional group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. can be exemplified.
  • Silane coupling agents having an epoxy group as a functional group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4 -epoxycyclohexyl)ethyltrimethoxysilane.
  • Silane coupling agents having an amino group as a functional group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropylethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N -2-(aminoethyl)-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, An example is N-(n-
  • silane-based surface modifier having one or more functional groups selected from vinyl groups such as methacryloxy, acryloxy, and styryl, amino groups, epoxy groups, and mercapto groups is used.
  • composition containing the copolymer and the surface modifier (hereinafter also simply referred to as "composition") can be prepared as follows.
  • these surface modifiers can be mixed by a known kneading method such as a twin-screw kneader, various rolls, and various kneaders.
  • the copolymer component is in the form of varnish, it can be mixed and dissolved by adding to the varnish and stirring.
  • the composition of the present invention further includes (a) a curing agent, (b) a hydrocarbon elastomer, a polyphenylene ether resin, and an aromatic polyene resin. Alternatively, it can contain one or more selected from a plurality of resins and (c) a polar monomer.
  • ⁇ (a) Curing agent> As the curing agent that can be used in the composition of the present invention, it is possible to use known radical generators and curing agents that can be conventionally used for polymerization or curing of aromatic polyenes and aromatic vinyl compounds. Examples of such curing agents include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators, and preferably radical polymerization initiators can be used. Organic peroxide-based (peroxide), azo-based polymerization initiators and the like are preferable, and can be freely selected according to the application and conditions. A catalog listing organic peroxides can be downloaded from the NOF website, for example, https://www.nof.co.jp/business/chemical/chemical-product01.
  • Organic peroxides are also described in the catalogs of Fuji Film Wako Pure Chemical Co., Ltd. and Tokyo Kasei Kogyo Co., Ltd., etc. Curing agents for use in the present invention are available from these companies.
  • a known photopolymerization initiator using light, ultraviolet rays, or radiation can also be used as a curing agent.
  • the curing agent using a photopolymerization initiator includes a photoradical polymerization initiator, a photocationic polymerization initiator, or a photoanion polymerization initiator.
  • photoinitiators are available, for example, from Tokyo Chemical Industry Co., Ltd.
  • curing by radiation or electron beam itself is also possible. It is also possible to crosslink and cure by heat of the raw material contained without containing a curing agent.
  • the amount of the curing agent used is not particularly limited, but is generally preferably 0.01 to 10 parts by weight per 100 parts by weight of the composition.
  • the composition preferably excludes curing agents and solvents.
  • a curing agent such as a peroxide or an azo polymerization initiator
  • the curing treatment is performed at an appropriate temperature and time in consideration of its half-life.
  • the conditions in this case are arbitrary according to the curing agent, but generally a temperature range of about 50°C to 200°C is suitable.
  • the total of component (b), that is, "one or more resins selected from hydrocarbon-based elastomers, polyphenylene ether-based resins, and aromatic polyene-based resins" is preferably based on 100 parts by mass of the copolymer It can be contained in the range of 1 to 200 parts by mass. Addition of these components (b) has the effect of improving the mechanical properties of the cured product obtained from the present varnish.
  • the amount of the hydrocarbon-based elastomer used in the composition of the present invention is preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and most preferably 1 to 50 parts by mass, relative to 100 parts by mass of the copolymer. .
  • the hydrocarbon elastomer that can be suitably used in the composition of the present invention preferably has a number average molecular weight of 100 or more and 100,000 or less, more preferably 1,000 or more and 4,500 or less.
  • the hydrocarbon-based elastomer that can be suitably used in the composition of the present invention is preferably an ethylene-based or propylene-based elastomer, a conjugated diene-based polymer, an aromatic vinyl compound-conjugated diene-based block copolymer, or One or more elastomers selected from random copolymers and hydrides (hydrogenated products) thereof.
  • Ethylene-based elastomers include ethylene- ⁇ -olefin copolymers such as ethylene-octene copolymers and ethylene-1-hexene copolymers, EPR, and EPDM.
  • Propylene-based elastomers include atactic polypropylene, low-stereoscopic Propylene- ⁇ -olefin copolymers such as regular polypropylene and propylene-1-butene copolymers can be mentioned. These hydrocarbon-based elastomers may be modified such as by introducing a functional group by reacting with a compound such as maleic anhydride.
  • Conjugated diene polymers include polybutadiene and 1,2-polybutadiene.
  • aromatic vinyl compound-conjugated diene block copolymers or random copolymers and hydrides (hydrogenated products) thereof include SBS, SIS, SEBS, SEPS, SEEPS and SEEBS.
  • 1,2-Polybutadiene that can be preferably used is available, for example, from Nippon Soda Co., Ltd. under the product names of Liquid Polybutadiene: Product Names B-1000, 2000, and 3000.
  • "Ricon 100" manufactured by TOTAL CRAY VALLEY can be exemplified.
  • conjugated diene polymers and their hydrides may be modified by introducing functional groups with compounds such as maleic anhydride.
  • one or more resins selected from these hydrocarbon-based elastomers are liquid (approximately 300,000 mPa s or less) at room temperature (25° C.), handleability and moldability in an uncured state (thermoplastic resin From the viewpoint of handling), the amount used is preferably 150 parts by mass or less, more preferably 1 to 30 parts by mass, and most preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer.
  • polyphenylene ether also referred to as "polyphenylene ether-based resin"
  • polyphenylene ether-based resin commercially available known polyphenylene ethers can be used.
  • the number average molecular weight of the polyphenylene ether is arbitrary, and is preferably 10,000 or less, most preferably 5,000 or less, in consideration of the molding processability of the composition.
  • the number average molecular weight is preferably 500 or more.
  • the terminal of the molecule is modified with a functional group.
  • one molecule has a plurality of functional groups.
  • modified polyphenylene ether is preferred.
  • the functional group includes a radically polymerizable functional group and a functional group such as an epoxy group, preferably a radically polymerizable functional group.
  • a vinyl group is preferable as the radically polymerizable functional group.
  • the vinyl group is preferably one or more selected from the group consisting of an allyl group, a (meth)acryloyl group and an aromatic vinyl group, more preferably one or more selected from the group consisting of a (meth)acryloyl group and an aromatic vinyl group.
  • groups are most preferred. That is, in the composition of the present invention, a bifunctional polyphenylene ether in which both ends of the molecular chain are modified with radically polymerizable functional groups is particularly preferred.
  • polyphenylene ethers examples include SABIC's Noryl (trademark) SA9000 (modified polyphenylene ether having methacryloyl groups at both ends, number average molecular weight of 2200) and Mitsubishi Gas Chemical Company's bifunctional polyphenylene ether oligomer (OPE-2St, both ends modified polyphenylene ether having a vinylbenzyl group, number average molecular weight 1200), and the like. Allylated PPE from Asahi Kasei can also be used. Among these, a bifunctional polyphenylene ether oligomer (OPE-2St) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.
  • the amount of polyphenylene ether used in the composition of the present invention is preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the copolymer.
  • the aromatic polyene-based resin includes divinylbenzene-based reactive hyperbranched copolymers (PDV, ODV) manufactured by Nippon Steel Chemical & Materials. Such multi-branched copolymers are described, for example, in the literature "Synthesis of Polyfunctional Aromatic Vinyl Copolymer and Development of New IPN-type Low Dielectric Loss Material Using Same” (Masao Kawabe et al., Journal of Electronics Packaging Society, pp. 125-129). , Vol.12 No.2 (2009)), U.S. Pat.
  • the aromatic polyene-based resins also include aromatic polyene polymer resins having the above-mentioned aromatic polyene monomer as a main structural unit.
  • the amount of the aromatic polyene resin used in the composition of the present invention is preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, most preferably 1 to 50 parts by mass, relative to 100 parts by mass of the copolymer. preferable.
  • the use of the aromatic polyene resin in an amount within these ranges is effective in adjusting the mechanical properties of the cured product obtained from the composition, and is preferable for preventing deterioration in adhesion to other members and deterioration in toughness. When it is 200 parts by mass or less, brittleness is not exhibited and adhesion to other members is improved.
  • the polar monomer that can be used in the composition of the present invention is preferably 100 parts by mass or less per 100 parts by mass of the copolymer.
  • the present composition may be substantially free of monomers.
  • the polar monomer is a monomer having one or more atoms selected from oxygen, nitrogen, phosphorus, and sulfur in the molecule, and the polar monomer that can be suitably used preferably has a molecular weight of less than 5000. , less than 1000, and even more preferably less than 500.
  • a polar monomer that can be suitably used in the composition of the present invention is preferably a polar monomer that can be polymerized by a radical polymerization initiator.
  • Polar monomers include various maleimides, bismaleimides, maleic anhydride, triallyl isocyanurate, glycidyl (meth)acrylate, tri(meth)acrylic isocyanurate, trimethylolpropane tri(meth)acrylate, and the like. be done.
  • Maleimides and bismaleimides that can be used in the present invention are described in, for example, International Publication No. 2016/114287 and Japanese Patent Application Laid-Open No. 2008-291227. can be purchased from inc.
  • Bismaleimide resin "SLK” manufactured by Shin-Etsu Chemical Co., Ltd. can also be used.
  • maleimide group-containing compounds are preferably bismaleimides from the viewpoints of solubility in organic solvents, high-frequency characteristics, high adhesion to conductors, moldability of prepreg, and the like.
  • These maleimide group-containing compounds may be used as polyaminobismaleimide compounds from the viewpoints of solubility in organic solvents, high frequency characteristics, high adhesion to conductors, moldability of prepreg, and the like.
  • a polyaminobismaleimide compound is obtained, for example, by Michael addition reaction between a compound having two maleimide groups at the terminals and an aromatic diamine compound having two primary amino groups in the molecule.
  • a polar monomer having a multifunctional group of two or more functional groups such as bismaleimides, triallyl isocyanurate (TAIC), trimethylolpropane tri ( Meth)acrylates can be exemplified.
  • the amount of the polar monomer used in the composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the copolymer. By using an amount within this range, the effect of preventing the dielectric constant and dielectric loss tangent of the resulting cured product from becoming too high can be obtained. 005 or less, preferably 0.002 or less.
  • the composition of the present invention can be appropriately added with an "aromatic vinyl compound” such as styrene, an "aromatic polyene” such as divinylbenzene, and an "aromatic vinylene compound".
  • an aromatic vinyl compound such as styrene, an "aromatic polyene” such as divinylbenzene, and an "aromatic vinylene compound”.
  • the amount of these additives to be added is arbitrary, but is preferably 100 parts by mass or less per 100 parts by mass of the copolymer.
  • the aromatic vinylene compound refers to a compound having both a single aromatic ring or a plurality of condensed aromatic rings having 9 to 30 carbon atoms and a vinylene group. Examples of such aromatic vinylene compounds include indenes, beta-substituted styrenes, acenaphthylenes, and the like.
  • indenes examples include indene, various alkyl-substituted indenes and phenyl-substituted indenes.
  • Beta-substituted styrenes include ⁇ -alkyl-substituted styrenes such as ⁇ -methylstyrene, phenyl-substituted styrenes, and the like.
  • Acenaphthylenes include acenaphthylene, various alkyl-substituted acenaphthylenes, various phenyl-substituted acenaphthylenes, and the like.
  • aromatic vinylene compound the above-exemplified compounds may be used alone, or two or more thereof may be used in combination.
  • the aromatic vinylene compound preferably has a boiling point of 175°C or higher at normal pressure. From the viewpoint of industrial availability and radical polymerizability, acenaphthylene is most preferable as the aromatic vinylene compound.
  • composition of the present invention may further contain one or more selected from (d) fillers and (e) flame retardants.
  • a known inorganic or organic filler can be added as required. These fillers are added for the purpose of controlling the coefficient of thermal expansion, controlling the thermal conductivity, and reducing the price, and the amount used is arbitrary depending on the purpose.
  • a known surface modifier such as a silane coupling agent.
  • the inorganic filler is preferably one or more of boron nitride (BN) or silica. , silica is more preferred. As silica, fused silica is preferred.
  • the average particle size (d50) of the filler is preferably 0.01-100 ⁇ m, more preferably 0.1-10 ⁇ m, most preferably 0.3-1 ⁇ m. d50 is the value at 50% cumulative volume.
  • the average particle size (d50) is obtained from a volume particle size distribution curve obtained from a laser diffraction particle size analyzer (Beckman Coulter "Model LS-230" type).
  • the specific surface area is preferably 1-30 m 2 /g, more preferably 3-10 m 2 /g.
  • a specific surface area is measured by the following method. A measurement cell is filled with 1 g of a sample, and the specific surface area is measured using a Macsorb HM model-1201 full-automatic specific surface area measuring device (BET single point method) manufactured by Mountaintech. The degassing condition before measurement is 200° C.-10 minutes. Nitrogen is used as the adsorbed gas.
  • the volume ratio of the resin component to the filler is in the range of 98-15:2-85, preferably 85-15:15-85, more preferably 85-30:15-70. , more preferably in the range of 80-60:20-40.
  • organic filler such as high-molecular-weight polyethylene or ultra-high-molecular-weight polyethylene instead of the inorganic filler.
  • the organic filler itself is preferably crosslinked, and is preferably blended in the form of fine particles or powder.
  • the composition of the present invention preferably has a dielectric constant of 4 to 10,000, more preferably 5 to 10,000 at 1 GHz.
  • a dielectric constant 4 to 10,000, more preferably 5 to 10,000 at 1 GHz.
  • An insulating layer with a high dielectric constant and a low dielectric loss tangent is suitable for applications such as capacitors, inductors for resonant circuits, filters, and antennas.
  • Examples of the high dielectric constant insulator filler used in the present invention include inorganic fillers and metal particles subjected to insulation treatment. Specific examples are known high dielectric constant inorganic fillers such as barium titanate and strontium titanate, and other examples are specifically described in JP-A-2004-087639.
  • Flame retardants may be used in the compositions of the present invention.
  • Preferred flame retardants are one or more selected from organophosphorus flame retardants such as phosphate esters or condensates thereof, brominated flame retardants, and red phosphorus from the viewpoint of maintaining a low dielectric constant and a low dielectric loss tangent.
  • organophosphorus flame retardants such as phosphate esters or condensates thereof, brominated flame retardants, and red phosphorus from the viewpoint of maintaining a low dielectric constant and a low dielectric loss tangent.
  • phosphoric acid esters compounds having a plurality of xylenyl groups in the molecule are particularly preferred from the viewpoint of flame retardancy and low dielectric loss tangent.
  • antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, etc., or melamine, triallyl-1,3,5-triazine-2,3,4-( Nitrogen-containing compounds such as 1H,3H,5H)-trione and 2,4,6-triaryloxy-1,3,5-triazine may be added.
  • the total amount of these flame retardants and auxiliary flame retardants is preferably 1 to 100 parts by mass per 100 parts by mass of the composition. Further, 30 to 200 parts by mass of the polyphenylene ether (PPE)-based resin having a low dielectric constant and excellent flame retardancy may be used with respect to 100 parts by mass of the flame retardant.
  • PPE polyphenylene ether
  • composition of the present invention may further contain (f) a solvent.
  • a solvent particularly liquid by containing a solvent.
  • a suitable solvent may be added to the composition of the present invention, if necessary. Moreover, the usage amount is not particularly limited. A solvent is used to adjust the viscosity and fluidity of the composition. Especially when the composition of the present invention is in the form of a varnish, a solvent is preferably used. As the solvent, if the boiling point under atmospheric pressure is too low, that is, if the volatility is too high, the thickness of the applied film may become uneven. A preferable boiling point is approximately 100° C. or higher, more preferably 110° C. or higher and 300° C. or lower under atmospheric pressure.
  • solvents examples include cyclohexane, toluene (boiling point 110° C.), ethylbenzene, xylene, mesitylene, tetralin, acetone, limonene, mixed alkanes, mixed aromatic solvents, and the like.
  • the amount of the solvent used in the composition of the present invention is arbitrary, but is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, most preferably 50 to 150 parts by mass, relative to 100 parts by mass of the copolymer. preferable.
  • composition and varnish of the present invention contain additives that are commonly used in resins, such as antioxidants, weathering agents, light stabilizers, lubricants, compatibilizers, and antistatic agents, as long as they do not impair the effects and purposes of the present invention. etc.
  • the composition and varnish of the present invention can be obtained by mixing, dissolving, or melting the various additives described above, and any known methods for mixing, dissolving, and melting can be employed.
  • the varnish of the present invention can be prepared at room temperature or 100°C by adjusting the composition and molecular weight of the copolymer to be used, adding a certain amount or more of a liquid monomer or solvent within the scope of the present invention, or adding a liquid flame retardant. It is possible to exhibit a viscous liquid state by heating as follows, for example, several hundred thousand mPa s or less at room temperature, preferably 2000 mPa s or less, more preferably 1000 mPa s or less, most preferably 500 mPa s. s or less viscosity.
  • viscosity is measured by, for example, a rotational viscometer.
  • a molded body can be obtained by applying, impregnating, filling, or dripping onto another material by an appropriate method and removing the solvent. Furthermore, the desired cured product can be obtained by curing with heat or light. Such properties can be obtained by various transfer molding (press-in molding), coating on or between substrates or semiconductor device materials, extrusion lamination, or spin coating to form sheets or films and then curing. Thus, a multilayer structure including the insulating layer I can be formed.
  • the molded article of the insulating layer obtained from the composition of the present invention is in the form of a sheet. Its thickness is arbitrary, but preferably in the range of 10 ⁇ m to 1 mm. These compositions can exhibit thermoplastic properties. Therefore, it can be molded into a shape such as a sheet in a substantially uncured state by a known molding method for thermoplastic resins, such as extrusion molding, injection molding, press molding, inflation molding, etc., under conditions that do not cause cross-linking. can be subsequently laminated with other layers and crosslinked (cured).
  • the composition when it is a varnish, it is applied to another substrate such as a smooth surface of a copper foil, and then the solvent is removed by heating, decompression, air drying, etc. to form a sheet or film shaped molded body, which is then laminated. It can be crosslinked (cured). It is also possible to impregnate a porous substrate, woven fabric, or non-woven fabric with the varnish of the present invention, remove the solvent, obtain a composite sheet, and use this as the multilayer structure. These sheets may be uncured (semi-cured) to the extent that the sheet shape can be maintained, or may be completely cured. The degree of hardening of the composition can be quantitatively measured by a known dynamic viscoelasticity measurement method (DMA, Dynamic Mechanical Analysis).
  • DMA Dynamic Mechanical Analysis
  • Curing of the above-described multilayer structure can be performed by a known method with reference to the curing conditions (temperature, time, pressure, light) of the raw materials and curing agent contained.
  • curing conditions such as heating conditions can be determined with reference to the half-life temperature and the like generally disclosed for each peroxide.
  • the cured body of the multilayer structure of the present invention can be sufficiently cured, and the cured body of the insulating layer may have a gel content of 90% by mass or more as measured according to ASTM.
  • the dielectric constant of the cured product of the present insulating layer is preferably 3.0 or less and 2.0 or more, more preferably 2.8 or less and 2.0 or more, in a measurement range of 10 to 50 GHz, particularly preferably at 10 GHz. 5 or less and 2.0 or more is most preferable.
  • the dielectric loss tangent is preferably 0.003 or less and 0.0005 or more, more preferably 0.002 or less and 0.0008 or more.
  • the hardened body of the insulating layer to be obtained preferably has a volume resistivity of 1 ⁇ 10 15 ⁇ cm or more and a water absorption of 0.1% by mass or less, which is preferable as an electrical insulating material. These values are particularly preferable values for an electrical insulating material for high frequencies of 3 GHz or higher, for example.
  • the cured insulating layer contained in the multilayer structure has high adhesiveness even to the smooth surface of the copper foil for wiring.
  • the adhesive strength is preferably 0.8 N/mm or more, more preferably 1.0 N/mm or more. Therefore, it is particularly preferable as an interlayer insulating material or a coverlay. At least a part or at least one surface of an interlayer insulating material used for multi-layer CCL or FCCL needs to be adhered to the smooth surface of the copper foil.
  • the cured product of the above composition exhibits high adhesiveness to the smooth surface of the copper foil, and is therefore preferred for its use.
  • the cured product of the present composition is also preferable because it exhibits high adhesion to the smooth surface of the copper foil.
  • Examples of methods for manufacturing high-frequency transmission lines, antennas, and multilayer substrates (CCL, FCCL) having a multilayer structure of the present invention include the following methods.
  • a composition was applied as a varnish on a substrate (resin layer) having a copper foil smooth surface open to the upper surface by adhering to the copper foil rough surface, and the solvent was removed to form an insulating layer.
  • another resin layer is superimposed to form a multi-layer structure, which is then treated under appropriate temperature and pressure conditions, cured and adhered to form a multi-layer substrate.
  • an uncured sheet prepared in advance is placed as an insulating layer on a substrate (resin layer) that has a smooth copper foil surface open to the top by adhering to the roughened surface of the copper foil.
  • another resin layer may be superimposed to form a multi-layer structure, which is treated under appropriate temperature and pressure conditions, cured and bonded to form a multi-layer substrate.
  • Examples of methods for manufacturing a substrate having a coverlay include the following processes.
  • a composition is applied as a varnish on a substrate that has a copper foil smooth surface open to the upper surface by adhering to the copper foil rough surface, the solvent is removed, and then pressurized and heated under predetermined conditions. and curing the insulating layer to form a coverlay.
  • an uncured sheet of the composition prepared in advance is superimposed on a substrate that has a smooth copper foil surface that is open to the top by adhering to the roughened surface of the copper foil, and pressurized and heated.
  • a method of curing and adhering the insulating layer can also be exemplified.
  • the present invention contains an olefin-aromatic vinyl compound-aromatic polyene copolymer as a main component, and 0.00 of a silane coupling agent is added to the olefin-aromatic vinyl compound-aromatic polyene copolymer.
  • a silane coupling agent is added to the olefin-aromatic vinyl compound-aromatic polyene copolymer.
  • 001 to 10 parts by mass of a cured composition and can provide high-frequency transmission lines such as microstrip lines, antennas, multilayer CCL substrates, or multilayer FCCL substrates containing the interlayer insulation material.
  • This interlayer insulating material layer is an interlayer insulating material having at least a portion thereof or one surface thereof in contact with the smooth surface of the copper foil. A layer of this interlayer insulating material is characterized by good low dielectric performance, heat resistance, and high adhesion to the copper foil smooth surface of the substrate.
  • the present invention contains an olefin-aromatic vinyl compound-aromatic polyene copolymer as a main component, and 0.00 of a silane coupling agent is added to the olefin-aromatic vinyl compound-aromatic polyene copolymer.
  • a silane coupling agent is added to the olefin-aromatic vinyl compound-aromatic polyene copolymer.
  • the present coverlay is characterized by the good low dielectric performance, heat resistance, and high adhesion to the copper foil smooth surface of the substrate.
  • a known method can be used to bond the insulating layer of the present invention to a resin layer made of other resin materials used in CCL or FCCL.
  • a method of activating the surface by subjecting the resin layer to corona treatment or plasma treatment in advance, or a method of roughening the surface by forming unevenness on the surface can be exemplified.
  • the insulating layer made of the composition of the present invention can be, for example, polyimide (PI), liquid crystal polymer (LCP), polyphenylene ether (PPE), polyfunctional aromatic vinyl resin (ODV), epoxy resin, or the same composition as insulating layer I. It is possible to exhibit a higher adhesive strength to each resin of a product and its sheet as compared with the case where no surface modifier is added. In particular, higher adhesiveness can be expected when the surface of these resin sheets is treated by surface treatment such as corona treatment or plasma treatment as described above.
  • the content of vinyl group units derived from ethylene, hexene, styrene, and divinylbenzene in the copolymer was determined by 1 H-NMR from peak area intensities attributed to each. Samples were dissolved in heavy 1,1,2,2-tetrachloroethane and measurements were made at 50-130°C.
  • GPC gel permeation chromatography
  • the cavity resonator perturbation method 822ES network analyzer manufactured by Agilent Technologies, cavity resonator manufactured by Kanto Denshi Applied Development Co., Ltd.
  • the copper foil used was manufactured by Mitsui Kinzoku Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 ⁇ m, roughened surface roughness Rz 1.1 ⁇ m).
  • the smooth surface of the copper foil is placed on a Teflon (registered trademark) sheet, and several uncured sheets, which are the insulating layer I, are placed on the smooth surface, and a SUS formwork (thickness 0.2 mm) is placed thereon.
  • the insulating layer I is an uncured sheet of Examples and Comparative Examples which will be described later.
  • the Teflon sheet and the formwork were removed, and a multi-layer structure was obtained by bonding and curing the sheet and the copper foil.
  • Adhesive strength measurement with copper foil was conducted according to Japanese Industrial Standards (JIS) C6471:1995, and peeling was evaluated by 180° peeling.
  • the copper foil roughened surface is placed on the Teflon sheet, and several uncured sheets are stacked on the roughened surface to form a laminated body that has been adhesively cured with the copper foil roughened surface.
  • the adhesion strength was measured in the same manner.
  • Difunctional polyphenylene ether oligomer (OPE-2St, number average molecular weight 1200) is obtained by further diluting the toluene solution product manufactured by Mitsubishi Gas Chemical Co., Ltd. with toluene, adding a large amount of methanol to precipitate methanol, air drying, and drying under reduced pressure. By doing so, a powdery polyphenylene ether oligomer was obtained and used.
  • As the 1,2-polybutadiene "B-3000” manufactured by Nippon Soda Co., Ltd., having a number average molecular weight of 3200 and a viscosity of 210 Poise (21000 mPa ⁇ s, 45° C.) was used.
  • BMI-5100 (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • Silane coupling agents are KBM-503 (3-methacryloxypropyltrimethoxysilane), KBM-403 (3-glycidoxypropyltrimethoxysilane), and KBM-1403 (p-styryltrimethoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd. was used.
  • Perhexyne 25B organic peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3) manufactured by NOF Corporation was used as a curing agent.
  • Example 1 P-1 (ethylene-styrene-divinylbenzene copolymer) obtained in Synthesis Example, solvent (toluene), and silane coupling agent KBM-503 in Table 2 were prepared using a vessel equipped with a heating and cooling jacket and a stirring blade. The mixture was heated to about 40° C. and stirred to dissolve the copolymer. Furthermore, 1 part by mass of a curing agent (dicumyl peroxide) was added to 100 parts by mass of the resin component excluding the curing agent, solvent and silane coupling agent, dissolved and mixed with stirring to obtain a varnish-like composition.
  • a curing agent dicumyl peroxide
  • the resulting composition was poured into a silicon mold (frame portion length 7 cm, width 7 cm, thickness 0.5 mm, 1.0 mm, or 2.0 mm) on a Teflon sheet placed on a glass plate, and air-dried. Furthermore, it was dried in a vacuum dryer at 60° C. for 3 hours or more to obtain an uncured sheet. Furthermore, the obtained uncured sheet is placed on a Teflon sheet and a SUS mold under a load of 5 MPa with a press, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 120 minutes. A cured sheet was obtained by removing the sheet and the SUS formwork.
  • Tables 2 and 3 show the gel content, dielectric constant, dielectric loss tangent, water absorption and volume resistivity of the cured sheet. Further, the adhesive strength at the interface of the cured multilayer structure comprising the smooth surface of the copper foil and the insulating layer I was determined by the above method, and the results are shown in Tables 2 and 3.
  • the insulating layer I is the uncured sheet of Examples and Comparative Examples. In the case of the example, when the adhesive strength at the interface between the smooth surface of the copper foil and the insulating layer I was measured, the adhesive strength was too high, and when the value was 1 N/mm or more, the resin part broke (material failure) or stretched completely. , or breakage of the copper foil (material breakage) occurred.
  • the adhesive strength was 1 N/mm or more.
  • Comparative Examples 1 and 2 showed values of 0.4 N/mm and 0.3 N/mm, respectively.
  • the adhesive strength at the interface between the roughened surface of the copper foil and the insulating layer I was measured in the same manner. That is, the composition according to this example can provide a cured product exhibiting high adhesive strength to both the smooth surface and the roughened surface of the copper foil.
  • silica filler was used with respect to 70 vol % (volume %) of the resin component. 1 part by mass of the curing agent was added to a total of 100 parts by mass of resin raw materials other than the curing agent, solvent, silane coupling agent and filler.
  • Example 11 Structure (2) shown in FIG. 2 was created.
  • the resin layer A was made of polyimide
  • the insulating layer I and the resin layer B were made of a composition containing the copolymer of the present invention.
  • a multilayer sheet (commercial product, Upicel N, polyimide film 25 ⁇ m, electrolytic copper foil 18 ⁇ m, single-sided copper-clad type) was prepared in which the roughened surface of copper foil was adhered to a polyimide (PI) sheet. Furthermore, an uncured sheet having a thickness of 500 ⁇ m obtained in the same manner as in Example 10 was prepared.
  • a copper foil manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP) was used.
  • Example 10 An uncured sheet obtained in the same manner as in Example 5, having a thickness of 100 ⁇ m (insulating layer I) is placed, and an uncured sheet (resin layer B) having a thickness of 100 ⁇ m obtained in Example 10 is placed on the uncured sheet.
  • a copper foil was placed so as to make contact.
  • a thin Teflon sheet is partially inserted between the smooth surface of the copper foil and the uncured sheet (insulating layer I) of Example 5, and cured under the same conditions as in Example 1 under pressure with a press.
  • a multilayer structure sheet was obtained in which layer A (polyimide)/copper foil/insulating layer I/resin layer B (Example 10)/copper foil were laminated and bonded in this order.
  • the inserted Teflon sheet was pulled out to trigger a tensile test, and the adhesive strength between the smooth surface of the copper foil and the insulating layer I was determined.
  • a thin Teflon sheet was partially inserted between the insulating layer I and the resin layer B, and the adhesive strength between the insulating layer I and the resin layer B of the multilayer structure sheet obtained by curing in the same manner was determined.
  • any sample exhibited an adhesive strength of 1 N/mm or more, breakage (material breakage) or stretching of the resin portion, or breakage (material breakage) of the copper foil occurred.
  • the adhesive strength between the smooth surface of the copper foil and the insulating layer I and between the insulating layer I and the resin layer B were both 1 N/mm or more.
  • the adhesive strength between the commercially available polyimide (PI) and the roughened surface of the copper foil, which was separately measured, was 1 N/mm or more. From the above, it can be seen that the multilayer structure of the present invention has strong adhesive strength between interfaces.
  • Example 12 A structure (4) shown in FIG. 3 was created.
  • the insulating layer I was made of a composition containing the copolymer of the present invention, and the resin layers A and B were both made of polyimide (PI).
  • PI polyimide
  • a multilayer structure sheet laminated and adhered was obtained.
  • a thin Teflon sheet was partially inserted between the smooth surface of the copper foil and the uncured sheet (insulating layer I) of Example 6 before curing, and the thin Teflon sheet was pulled out for a tensile test. , and the adhesion strength between the smooth surface of the copper foil and the insulating layer I was determined.
  • breakage material breakage of the resin portion occurred when the adhesive strength was 1 N/mm or more. That is, the adhesive strength between the smooth surface of the copper foil and the insulating layer I was 1 N/mm or more.
  • Example 13 A basic unit structure shown in FIG. 1 was created.
  • the insulating layer I was made of the copolymer composition of the present invention, and the resin layer A was made of polyimide.
  • a multilayer sheet commercial product, the same as in Example 11
  • PI polyimide
  • a cured sheet having a thickness of 500 ⁇ m (insulating layer I) was placed, and a thin Teflon sheet was partially inserted between the smooth surface of the copper foil and the uncured sheet (insulating layer I).
  • a cured sheet having a multi-layer structure consisting of resin layer A (polyimide)/copper foil/insulating layer I was obtained.
  • the tension test was triggered by pulling out the inserted Teflon sheet, and the adhesion strength between the smooth surface of the copper foil and the insulating layer I was determined.
  • the adhesive strength was 1 N/mm or more, breakage (material breakage) or stretching of the resin portion, or breakage (material breakage) of the copper foil occurred. That is, the adhesive strength between the smooth surface and the insulating layer I was 1 N/mm or more.
  • Example 14 A basic unit structure shown in FIG. 1 was created.
  • a copper foil manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP) was used.
  • both the insulating layer I and the resin layer A were made of the composition of the copolymer of the present invention.
  • the adhesive strength was 1 N/mm or more, breakage (material breakage) or stretching of the resin portion, or breakage (material breakage) of the copper foil occurred. That is, the adhesive strength between the smooth surface and the insulating layer I was 1 N/mm or more.
  • a cured insulating layer made of the composition of the present invention exhibits a high gel content, is sufficiently cured, and can exhibit a low dielectric constant, a low dielectric loss tangent, a low water absorption, and a high resistivity.
  • the multi-layer cured product of the present invention can exhibit high adhesive strength not only to the rough surface of the copper foil but also to the smooth surface of the copper foil. Therefore, it is possible to have high adhesiveness between each layer, and the cured body of this multilayer structure is useful as an interlayer insulation layer (interlayer insulation material) or coverlay for high frequency transmission lines, multilayer CCLs, multilayer FCCLs, or antennas. be.

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EP22881052.9A EP4417413A4 (en) 2021-10-14 2022-10-12 MULTILAYER STRUCTURE INCLUDING AN INSULATING LAYER
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192392A (ja) 1992-12-24 1994-07-12 Sumitomo Bakelite Co Ltd 低誘電率熱硬化性樹脂組成物
JPH0940709A (ja) 1995-07-31 1997-02-10 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体の製造方法
JPH09309925A (ja) 1996-03-19 1997-12-02 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体及びその製造方法
JP2004087639A (ja) 2002-08-26 2004-03-18 Hitachi Ltd 低誘電正接絶縁材料を用いた高周波用電子部品
JP2007217706A (ja) 1998-12-22 2007-08-30 Denki Kagaku Kogyo Kk クロス共重合化オレフィン−スチレン−ジエン共重合体、その製造方法及びその用途
JP2008291227A (ja) 2007-04-26 2008-12-04 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂を含有する樹脂ワニスの製造方法、並びにこれを用いたプリント配線板用樹脂ワニス、プリプレグ及び金属張積層板
JP2009161743A (ja) 2007-12-10 2009-07-23 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた高周波用電気絶縁材料
JP2010280771A (ja) 2009-06-03 2010-12-16 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた電気絶縁材料
US8404797B2 (en) 2008-03-04 2013-03-26 Nippon Steel Chemical Co., Ltd. Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition
WO2016114287A1 (ja) 2015-01-13 2016-07-21 日立化成株式会社 フレキシブルプリント配線板用樹脂フィルム、樹脂付き金属箔、カバーレイフィルム、ボンディングシート及びフレキシブルプリント配線板
WO2018181842A1 (ja) 2017-03-30 2018-10-04 新日鉄住金化学株式会社 可溶性多官能ビニル芳香族共重合体、その製造方法並びに硬化性樹脂組成物及びその硬化物
WO2021112087A1 (ja) 2019-12-03 2021-06-10 デンカ株式会社 共重合体及びこれを含む積層体
WO2022014599A1 (ja) * 2020-07-15 2022-01-20 デンカ株式会社 組成物及び硬化体
WO2022054885A1 (ja) * 2020-09-11 2022-03-17 デンカ株式会社 組成物及びその硬化体
JP2022085610A (ja) * 2020-11-27 2022-06-08 デンカ株式会社 組成物及びその硬化物

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001287300A (ja) * 2000-04-04 2001-10-16 Shin Etsu Polymer Co Ltd 銅張積層基板及びその製造方法
JP2002353633A (ja) * 2001-05-25 2002-12-06 Shin Kobe Electric Mach Co Ltd 多層プリント配線板の製造法及び多層プリント配線板
KR100815319B1 (ko) * 2006-08-30 2008-03-19 삼성전기주식회사 고밀도 인쇄회로기판 및 그 제조 방법
JP2011074187A (ja) 2009-09-30 2011-04-14 Denki Kagaku Kogyo Kk 易架橋性熱可塑性樹脂
JP6601675B2 (ja) * 2016-01-14 2019-11-06 パナソニックＩｐマネジメント株式会社 金属張積層板および樹脂付金属箔
JP6738205B2 (ja) * 2016-06-06 2020-08-12 昭和電工パッケージング株式会社 ラミネート材
JP6995534B2 (ja) 2016-08-31 2022-01-14 日鉄ケミカル＆マテリアル株式会社 可溶性多官能ビニル芳香族共重合体、その製造方法、硬化性樹脂組成物及びその硬化物
CN109385018A (zh) * 2017-08-04 2019-02-26 广东生益科技股份有限公司 一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板
CN109385021A (zh) * 2017-08-04 2019-02-26 广东生益科技股份有限公司 一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192392A (ja) 1992-12-24 1994-07-12 Sumitomo Bakelite Co Ltd 低誘電率熱硬化性樹脂組成物
JPH0940709A (ja) 1995-07-31 1997-02-10 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体の製造方法
JPH09309925A (ja) 1996-03-19 1997-12-02 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体及びその製造方法
JP2007217706A (ja) 1998-12-22 2007-08-30 Denki Kagaku Kogyo Kk クロス共重合化オレフィン−スチレン−ジエン共重合体、その製造方法及びその用途
JP2004087639A (ja) 2002-08-26 2004-03-18 Hitachi Ltd 低誘電正接絶縁材料を用いた高周波用電子部品
JP2008291227A (ja) 2007-04-26 2008-12-04 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂を含有する樹脂ワニスの製造方法、並びにこれを用いたプリント配線板用樹脂ワニス、プリプレグ及び金属張積層板
JP2009161743A (ja) 2007-12-10 2009-07-23 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた高周波用電気絶縁材料
US8404797B2 (en) 2008-03-04 2013-03-26 Nippon Steel Chemical Co., Ltd. Polyfunctional vinyl aromatic copolymer, process for producing the same, and resin composition
JP2010280771A (ja) 2009-06-03 2010-12-16 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた電気絶縁材料
WO2016114287A1 (ja) 2015-01-13 2016-07-21 日立化成株式会社 フレキシブルプリント配線板用樹脂フィルム、樹脂付き金属箔、カバーレイフィルム、ボンディングシート及びフレキシブルプリント配線板
WO2018181842A1 (ja) 2017-03-30 2018-10-04 新日鉄住金化学株式会社 可溶性多官能ビニル芳香族共重合体、その製造方法並びに硬化性樹脂組成物及びその硬化物
WO2021112087A1 (ja) 2019-12-03 2021-06-10 デンカ株式会社 共重合体及びこれを含む積層体
WO2021112088A1 (ja) 2019-12-03 2021-06-10 デンカ株式会社 硬化性組成物及びその硬化体
WO2022014599A1 (ja) * 2020-07-15 2022-01-20 デンカ株式会社 組成物及び硬化体
WO2022054885A1 (ja) * 2020-09-11 2022-03-17 デンカ株式会社 組成物及びその硬化体
JP2022085610A (ja) * 2020-11-27 2022-06-08 デンカ株式会社 組成物及びその硬化物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MASAO KAWABE ET AL.: "Synthesis of polyfunctional aromatic vinyl copolymer and development of new lPN-type low dielectric loss material using same", JOURNAL OF ELECTRONICS PACKAGING SOCIETY, vol. 12, no. 2, 2009, pages 125 - 129
See also references of EP4417413A4

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