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WO2024161859A1 - Composition durcissable, feuille de résine, objet multicouche, stratifié revêtu de métal et carte de câblage - Google Patents

Composition durcissable, feuille de résine, objet multicouche, stratifié revêtu de métal et carte de câblage Download PDF

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Publication number
WO2024161859A1
WO2024161859A1 PCT/JP2023/046231 JP2023046231W WO2024161859A1 WO 2024161859 A1 WO2024161859 A1 WO 2024161859A1 JP 2023046231 W JP2023046231 W JP 2023046231W WO 2024161859 A1 WO2024161859 A1 WO 2024161859A1
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Prior art keywords
curable composition
mass
resin layer
parts
crosslinking agent
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Ceased
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PCT/JP2023/046231
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English (en)
Japanese (ja)
Inventor
祐輔 佐藤
元司 小野
和美 橋本
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AGC Inc
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Asahi Glass Co Ltd
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Publication of WO2024161859A1 publication Critical patent/WO2024161859A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—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
    • B32B27/00—Layered products comprising a layer 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • H05K1/03—Use of materials for the substrate

Definitions

  • This disclosure relates to a curable composition, a resin sheet, a laminate, a metal-clad laminate, and a wiring board.
  • Wiring boards are used for applications such as electrical and electronic devices. Wiring boards can be manufactured, for example, as follows. A fiber substrate is impregnated with a curable composition containing a curable polymer and, if necessary, additives such as a flame retardant and an inorganic filler (also called a filler), and the curable composition is (semi-)cured to produce a prepreg. One or more prepregs are sandwiched between a pair of metal foils, and the resulting first temporary laminate is heated and pressurized to produce a metal-clad laminate. The metal foil on the outermost surface of this metal-clad laminate is used to form a conductor pattern (also called a circuit pattern) such as wiring. The outermost metal foil may be placed on only one side of the first temporary laminate.
  • a curable composition containing a curable polymer and, if necessary, additives such as a flame retardant and an inorganic filler (also called a filler), and the curable composition is (semi
  • the resulting wiring board can be further laminated with one or more prepregs, sandwiched between a pair of metal foils, and the resulting second temporary laminate can be heated and pressurized to form a conductor pattern such as wiring using the metal foil on the outermost surface, thereby producing a multilayer wiring board (also called a multilayer printed wiring board).
  • the outermost metal foil may be placed on only one side of the second temporary laminate.
  • the heated and pressurized prepreg contains a fiber base material, a resin, an inorganic filler, etc., and is also called a core base material.
  • the core base material functions as an insulating layer.
  • the resin contained in the prepreg is a (semi-)cured product of the curable composition, and the resin contained in the wiring board is a cured product of the curable composition.
  • a wiring board used for this application is required to reduce transmission loss in the high frequency range.
  • Transmission loss mainly includes conductor loss caused by the surface resistance of metal foil and dielectric loss caused by the dielectric tangent ( Df ) of the resin.
  • a resin contained in a wiring board used for the above application is required to reduce dielectric loss in the high frequency range.
  • the dielectric tangent ( Df ) depends on the frequency, and for the same material, the higher the frequency, the larger the dielectric tangent ( Df ) tends to be. It is preferable that the resin contained in the wiring board has a low dielectric tangent ( Df ) under high frequency conditions.
  • the adhesion between the core substrate and the metal foil is important.
  • Conventionally there is a technique for roughening the surface of the metal foil on the core substrate side in order to improve the adhesion between the core substrate and the metal foil.
  • this technique is not preferable because it is prone to cause loss of high frequency current.
  • Components are mounted on the surface of the wiring board using solder. In order to ensure the reliability of the wiring board when mounting components, it is preferable that the resin contained in the wiring board has good heat resistance.
  • a resin layer capable of functioning as an adhesive layer can be provided between the core substrate and the metal foil.
  • This resin layer can be a cured product of a curable composition containing a curable polymer.
  • Patent Document 1 aims to provide a thermosetting composition which is suitable for use in metal-clad laminates and wiring boards, and which has a cured product having a low dielectric constant, a low dielectric tangent, high heat resistance, and high adhesion to resins.
  • thermosetting composition containing an ethylene-propylene-diene copolymer (A) and an inorganic filler (B) that has been surface-treated with a surface treatment agent having a polymerizable unsaturated bond (Claim 1).
  • the amount of the inorganic filler (B) is preferably 30 to 500 parts by mass per 100 parts by mass of the ethylene-propylene-diene copolymer (A) (claim 2).
  • the ethylene-propylene-diene copolymer (A) is a curable polymer, and the diene unit, which is a structural unit derived from a diene, contributes to curing (paragraph 0019).
  • the inorganic filler (B) can contribute to improving the heat resistance of the cured product.
  • the thermosetting composition is cured, the polymerizable unsaturated bond of the inorganic filler (B) reacts with the diene unit of the ethylene-propylene-diene copolymer (A), thereby increasing the crosslink density of the cured product and improving the heat resistance of the cured product (paragraph 0031).
  • thermosetting composition described in Patent Document 1 contains a large amount of the inorganic filler (B) as one of the essential components, and preferably contains 30 parts by mass or more of the inorganic filler (B) per 100 parts by mass of the ethylene-propylene-diene copolymer (A).
  • a large amount of the inorganic filler (B) is difficult to disperse well in the composition and is prone to agglomeration in the composition, making it difficult to prepare a uniform composition and difficult to apply the composition thinly and uniformly to the surfaces of various substrates.
  • thermosetting composition containing a large amount of inorganic filler (B) tends to have reduced adhesion to various substrates (also referred to as substrate adhesion) and a high (i.e., deteriorated) dielectric tangent ( Df ) under high frequency conditions.
  • the present disclosure has been made in consideration of the above circumstances, and aims to provide a curable composition that can obtain a resin having a reduced inorganic filler content, effectively reducing the dielectric tangent (D f ) under high frequency conditions, and having good heat resistance and adhesion to substrates.
  • thermoplastic elastomers selected from the group consisting of block copolymers including one or more polymer blocks (A) composed of structural units derived from one or more aromatic vinyl compounds including one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, and one or more polymer blocks (B) composed of structural units derived from one or more conjugated diene compounds, and hydrogenated products of the block copolymers; 2.5 to 30 parts by mass of a crosslinking agent (C) having a hetero atom per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C); 0 to 25 parts by mass of an inorganic filler (F) relative to 100 parts by mass in total of the thermoplastic elastomer (E) and the crosslinking agent (C); and a radical polymerization initiator (I),
  • a curable curable polymer blocks A
  • A composed of structural units derived from one or more aromatic vinyl compounds including one or more alkylst
  • R1 and R2 each independently represent a hydrocarbon group which may have a substituent.
  • a resin sheet comprising a dried product, a semi-cured product or a cured product of the curable composition according to any one of [1] to [9].
  • [12] A laminate comprising a substrate and a resin layer made of a dried product, a semi-cured product, or a cured product of the curable composition according to any one of [1] to [9].
  • the thickness of the resin layer is t [ ⁇ m] and the amount of the crosslinking agent (C) in the curable composition is q [parts by mass] relative to 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C)
  • the laminate of [12] wherein t [ ⁇ m] is 0.1 to 50 and t ⁇ q [ ⁇ m parts by mass] is 40 or less.
  • a metal-clad laminate having a core substrate and a metal foil laminated on at least one surface of the core substrate, A metal-clad laminate having a resin layer between the core substrate and the metal foil, the resin layer being made of a cured product of the curable composition of any one of [1] to [9].
  • a wiring board having a core substrate and wiring formed on at least one surface of the core substrate, A wiring board having a resin layer between the core substrate and the wiring, the resin layer being made of a cured product of the curable composition of any one of [1] to [9].
  • a curable composition that can obtain a resin having a reduced inorganic filler content, effectively reducing the dielectric tangent ( Df ) under high frequency conditions, and having good heat resistance and adhesion to substrates.
  • FIG. 1 is a schematic cross-sectional view of a resin sheet according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view of a metal-clad laminate according to a first embodiment of the present invention.
  • FIG. FIG. 4 is a schematic cross-sectional view of a metal-clad laminate according to a second embodiment of the present invention.
  • 1 is a schematic cross-sectional view of a wiring board according to an embodiment of the present invention;
  • the terms “film” and “sheet” are used for thin film molded bodies depending on their thickness, but there is no clear definition of these terms and no clear distinction between them. In this specification, there is no clear distinction between a film and a sheet, and both are collectively referred to as a "sheet.”
  • the term “semi-cured” is a general term for semi-cured and fully cured.
  • the term “wiring board” includes a multilayer wiring board.
  • the "surface” of a sheet-like body such as a prepreg refers to the main surface having the largest area.
  • the term “polymer” includes homopolymers and copolymers.
  • the "alkyl group having 3 or more carbon atoms” may be either linear or branched.
  • compounds having isomers include all isomers.
  • the "weight average molecular weight (Mw)” is the weight average molecular weight calculated as standard polystyrene by gel permeation chromatography (GPC).
  • the "high frequency region” is defined as a region having a frequency of 1 GHz or higher.
  • the term "to" indicating a range of values is used to mean that the range includes the values before and after it as the lower and upper limits.
  • the curable composition of the present disclosure comprises: one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers comprising one or more polymer blocks (A) consisting of structural units derived from one or more aromatic vinyl compounds including one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, and one or more polymer blocks (B) consisting of structural units derived from one or more conjugated diene compounds, and hydrogenated products of the block copolymers; 2.5 to 30 parts by mass of a crosslinking agent (C) having a hetero atom per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C); and a radical polymerization initiator (I).
  • the curable composition of the present disclosure may contain 0 to 25 parts by weight of an inorganic filler (F) per 100 parts by weight of the total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • the curable composition of the present disclosure comprises one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers comprising one or more polymer blocks (A) consisting of structural units derived from one or more aromatic vinyl compounds including one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, and one or more polymer blocks (B) consisting of structural units derived from one or more conjugated diene compounds, and hydrogenated products of the block copolymers.
  • the polymer block (A) is a hard segment block
  • the polymer block (B) is a soft segment block.
  • the block copolymer can be an addition polymerization type block copolymer.
  • the number of polymer blocks in the block copolymer is not particularly limited.
  • the block copolymer can be a diblock copolymer, a triblock copolymer, a tetrablock copolymer, or a higher order multiblock copolymer.
  • a triblock copolymer is preferred.
  • the block arrangement is not particularly limited, and examples include AB, ABA, BAB, ABABA, and BABAB.
  • the compositions of the multiple polymer blocks (A) may be the same or different. The same applies when the block copolymer contains multiple polymer blocks (B).
  • the block copolymer may further contain one or more other polymer blocks other than those described above.
  • the thermoplastic elastomer (E) is preferably a hydrogenated product obtained by hydrogenating a block copolymer and removing at least a part of the residual unsaturated bonds of the block copolymer.
  • the one or more aromatic vinyl compounds which are raw material monomers for the polymer block (A) include one or more alkylstyrene compounds.
  • the aromatic vinyl compound When the aromatic vinyl compound has a structural isomer, it may be any of an ortho-isomer, a meta-isomer, and a para-isomer.
  • the alkylstyrene compound is a (C1-C8 alkyl)styrene compound having a benzene ring and an alkyl group having 1 to 8 carbon atoms bonded thereto.
  • the number of alkyl groups having 1 to 8 carbon atoms bonded to the benzene ring is not particularly limited, and may be either single or multiple.
  • the (C1-C8 alkyl)styrene compound includes o-, m-, or p-alkylstyrene, 2,4-dialkylstyrene, 3,5-dialkylstyrene, and 2,4,6-trialkylstyrene, etc.
  • the (C1-C8 alkyl)styrene compound may be a substituted alkylstyrene compound such as a halogenated alkylstyrene in which one or more hydrogen atoms in the alkyl group are replaced with a halogen atom.
  • (C1-C8 alkyl)styrene compound examples include o-, m-, or p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, o-, m-, or p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-, m-, or p-propylstyrene, 2,4-dipropylstyrene, 3,5-dipropylstyrene, 2,4,6-tripropylstyrene, 2-methyl-4-ethylstyrene, 3-methyl-5-ethylstyrene, o-, m-, or p-chloromethylstyrene, 2,4-bis(chloro
  • the content of structural units derived from a (C1-C8 alkyl)styrene compound in the polymer block (A) is not particularly limited, and is preferably 1 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, particularly preferably 20 mass% or more, and most preferably 30 mass% or more.
  • the content of structural units derived from a (C1-C8 alkyl)styrene compound in the polymer block (A) is preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less, and most preferably 60 mass% or less.
  • the "amount of polymer block (A)” refers to the total amount of the plurality of polymer blocks (A). The same applies to the polymer block (B).
  • the polymer block (A) may contain structural units derived from one or more aromatic vinyl compounds other than those mentioned above.
  • aromatic vinyl compounds other than those mentioned above include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, t-butylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, acetonaphthylene, and alkylstyrene compounds having an alkyl group with 9 or more carbon atoms. Among these, styrene is preferred.
  • the polymer block (A) may contain, in addition to the structural units derived from one or more aromatic vinyl compounds, structural units derived from one or more other copolymerizable monomers.
  • the content of structural units derived from an aromatic vinyl compound in the polymer block (A) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
  • the proportion of structural units derived from other copolymerizable monomers in the polymer block (A) is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and may be 0% by mass.
  • Examples of the other copolymerizable monomers include (meth)acrylic acid esters, 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and other monomers capable of ion polymerization.
  • (meth)acrylic is a general term for acrylic and methacrylic.
  • the polymer block (A) may contain one or more crosslinkable functional groups.
  • crosslinkable functional groups include active hydrogen atom-containing functional groups such as -OH, -SH, -NH 2 , -NHR, -CONH 2 , -CONHR, -CONH-, -SO 3 H, -SO 2 H, and -SOH; nitrogen atom-containing functional groups such as -NR 2 , >C ⁇ NH, >C ⁇ N-, -CN, -NCO, -OCN, -SCN, -NO, -NO 2 , -NCS, -CONR 2 , and -CONR-; (thio)carbonyl group-containing functional groups such as >C ⁇ O, >C ⁇ S, -CH ⁇ O, -CH ⁇ S, -COOR, and -CSOR;
  • R is a hydrocarbon group.
  • the crosslinkable functional group is preferably a non-polar atom-containing group that does not contain polar atoms such as nitrogen atoms, oxygen atoms, and sulfur atoms.
  • the constituent atoms of the crosslinkable functional group are preferably only carbon atoms and hydrogen atoms.
  • the arrangement of the multiple structural units is not particularly limited and may be any arrangement, such as an alternating arrangement, a block arrangement, a random arrangement, or a tapered block arrangement.
  • Conjugated diene compounds that are raw monomers for polymer block (B) include isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.
  • Preferred polymer blocks (B) are polyisoprene blocks, polybutadiene blocks, isoprene/butadiene copolymer blocks, and hydrogenated blocks in which at least some of the unsaturated bonds in these blocks have been hydrogenated.
  • the polymer block (B) may further contain structural units derived from one or more other copolymerizable monomers other than those mentioned above.
  • the content of the structural unit derived from the conjugated diene compound in the polymer block (B) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
  • the proportion of structural units derived from other copolymerizable monomers in the polymer block (B) is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, and may be 0% by mass.
  • the other copolymerizable monomers include styrene, p-methylstyrene, ⁇ -methylstyrene, and other monomers capable of ionically polymerizing.
  • the arrangement of the plurality of structural units is not particularly limited and may be any arrangement such as an alternating arrangement, a block arrangement, a random arrangement, or a tapered block arrangement.
  • the ratio of the mass of the polymer block (A) (total amount if there are multiple polymer blocks) to the mass of the polymer block (B) (total amount if there are multiple polymer blocks) is not particularly limited, but is preferably 5/95 to 85/15, more preferably 10/90 to 70/30, and particularly preferably 20/80 to 50/50.
  • the weight average molecular weight (Mw) of the thermoplastic elastomer (E) is not particularly limited. From the viewpoint of thin-wall coating properties of the curable composition, the Mw is preferably 50,000 to 1,000,000, more preferably 80,000 to 500,000, and particularly preferably 100,000 to 500,000.
  • the thermoplastic elastomer (E) can be produced by a known method, and a commercially available product can be used. Examples of the commercially available thermoplastic elastomer (E) include hydrogenated styrene-based thermoplastic elastomer "Septon (registered trademark) V series" manufactured by Kuraray Co., Ltd.
  • the thermoplastic elastomer (E) may have a structure in which the main chain does not contain a polar atom.
  • the thermoplastic elastomer (E) may have a structure that does not contain polar atoms or has a small amount of polar atoms. It is preferable that the thermoplastic elastomer (E) does not contain polar atoms.
  • the curable composition of the present disclosure includes one or more crosslinking agents (C) having a heteroatom.
  • the crosslinking agent (C) is a polyfunctional compound having a plurality of polymerizable functional groups in one molecule.
  • the polymerizable functional groups include groups having a polymerizable carbon-carbon unsaturated bond, epoxy groups, isocyanate groups, hydroxy groups, mercapto groups, amino groups, ureido groups, carboxy groups, sulfonic acid groups, acid chloride groups, and chlorine atoms.
  • the crosslinking agent (C) can increase the crosslink density of the cured product of the curable composition.
  • the crosslinking agent (C) can contribute to improving the toughness of the cured product, improving the glass transition temperature (Tg) (i.e., improving the heat resistance), reducing the linear expansion coefficient, and improving the adhesion to substrates.
  • Crosslinking agents that do not have heteroatoms and are composed only of carbon atoms and hydrogen atoms, such as 1,2-bis(p-vinylphenyl)ethane (BVPE), are not very compatible with the thermoplastic elastomer (E), and may cause poor appearance such as cloudiness and streaks in the dried and (semi-)cured products. In addition, due to poor compatibility, the effect of improving the heat resistance of the cured product may not be stably obtained.
  • the crosslinking agent (C) having a heteroatom has good compatibility with the thermoplastic elastomer (E), can suppress the appearance defect of the dried product and (semi-)cured product, and can stably improve the heat resistance of the cured product.
  • the heteroatom is a polar atom, the adhesion of the cured product to the substrate can be effectively improved.
  • the content of the crosslinking agent (C) in the curable composition of the present disclosure (the total amount when multiple types are used) is 2.5 parts by mass or more, preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • the content of the crosslinking agent (C) in the curable composition of the present disclosure is 30 parts by mass or less, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and most preferably 10 parts by mass or less, per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • crosslinking agents having heteroatoms can be used.
  • heteroatoms include nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur atoms, and combinations thereof.
  • crosslinking agents having heteroatoms (C) include bismaleimides and nitrogen-containing allyl compounds.
  • Examples of the nitrogen-containing allyl compound include triallyl isocyanurate (TAIC), a compound represented by the following formula (CX) (also referred to as compound (CX)), a compound represented by the following formula (CY) (also referred to as compound (CY)), and 1,3,4,6-tetraallyl glycoluril.
  • R 1 and R 2 are each independently a hydrocarbon group which may have a substituent.
  • R 1 has preferably 4 to 20 carbon atoms, more preferably 8 to 18 carbon atoms.
  • R 2 has preferably 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • the substituent which R 1 and R 2 may have may contain a heteroatom such as a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, or a combination thereof.
  • the crosslinking agent (C) preferably contains one or more nitrogen-containing allyl compounds selected from the group consisting of triallyl isocyanurate (TAIC), compound (CX), compound (CY), and 1,3,4,6-tetraallylglycoluril.
  • the crosslinking agent (C) can be one or more nitrogen-containing allyl compounds selected from the group consisting of triallyl isocyanurate (TAIC), compound (CX), compound (CY), and 1,3,4,6-tetraallylglycoluril.
  • the unsubstituted compound (CX) has a hydrocarbon group (R) such as an alkyl group that does not contain a polar atom, and therefore may be able to effectively reduce the dielectric tangent (D f ) of the cured product under high frequency conditions.
  • the compound (CY) and 1,3,4,6-tetraallyl glycol uril have a larger number of polymerizable functional groups than triallyl isocyanurate (TAIC) and the compound (CX). Therefore, the compound (CY) and/or 1,3,4,6-tetraallyl glycol uril may be able to effectively improve the adhesion of the cured product to a substrate in some cases.
  • the compound (CX) may have a phosphorus atom-containing substituent.
  • the cured product of the curable composition of the present disclosure containing the compound (CX) having a phosphorus atom-containing substituent can have good flame retardancy.
  • CX Commercially available products of compound (CX) include “L-DAIC” manufactured by Shikoku Kasei Corporation.
  • Commercially available products of compound (CX) having a phosphorus atom-containing substituent include “P-DAIC” manufactured by Shikoku Kasei Corporation.
  • Commercially available products of compound (CY) include "DD-1” manufactured by Shikoku Kasei Corporation.
  • Commercially available products of 1,3,4,6-tetraarylglycoluril include “TA-G” manufactured by Shikoku Kasei Corporation.
  • the crosslinking agent (C) can include one or more nitrogen-containing allyl compounds selected from the group consisting of compound (CX), compound (CY), and 1,3,4,6-tetraallylglycoluril.
  • the crosslinking agent (C) can be one or more nitrogen-containing allyl compounds selected from the group consisting of compound (CX), compound (CY), and 1,3,4,6-tetraallylglycoluril.
  • the crosslinking agent (C) may be a combination of triallyl isocyanurate (TAIC) and one or more nitrogen-containing allyl compounds selected from the group consisting of compound (CX), compound (CY), and 1,3,4,6-tetraallyl glycoluril. In this case, for example, a combination of triallyl isocyanurate (TAIC) and one or more compounds (CX) is preferred.
  • a laminate sheet with a protective film may be produced by applying the curable composition of the present disclosure containing an appropriate amount of an organic solvent (S) onto a substrate by a roll-to-roll process, drying the composition, forming a resin layer made of a dried product of the curable composition of the present disclosure, and then laminating a protective film thereon.
  • S organic solvent
  • TAIC triallyl isocyanurate
  • the crosslinking agent (C) contains triallyl isocyanurate (TAIC)
  • the amount of triallyl isocyanurate (TAIC) is 2.5 to 15 parts by mass and the amount of crosslinking agent (C) (total amount in the case of multiple types) is 2.5 to 17.5 parts by mass per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • the content of triallyl isocyanurate (TAIC) and the amount of crosslinking agent (C) in the curable composition of the present disclosure are within the above ranges, the development of tackiness in the dried product of the curable composition of the present disclosure is suppressed, and when a member such as a protective film is superimposed on a resin layer made of the dried product of the curable composition of the present disclosure, migration of the components of the resin layer to the member such as the protective film can be suppressed.
  • TAIC triallyl isocyanurate
  • C crosslinking agent
  • the curable composition of the present disclosure may contain only the thermoplastic elastomer (E) and the crosslinking agent (C) as the curable compounds.
  • the curable composition of the present disclosure may optionally contain one or more other curable compounds other than those described above.
  • curable compounds include curable compounds that, when cured alone, become resins such as polyphenylene ether resins (PPE), bismaleimide resins, epoxy resins, fluororesins, polyimides, polyolefins, polyesters, polystyrenes, hydrocarbon elastomers other than those mentioned above, benzoxazine resins, active ester resins, cyanate ester resins, butadiene resins, vinyl resins, cycloolefin polymers, aromatic polymers, and divinyl aromatic polymers.
  • PPE polyphenylene ether resins
  • bismaleimide resins epoxy resins
  • fluororesins polyimides
  • polyolefins polyesters
  • polystyrenes polystyrenes
  • hydrocarbon elastomers other than those mentioned above
  • benzoxazine resins active ester resins
  • cyanate ester resins butadiene resins
  • vinyl resins vinyl resins
  • curable compounds include, for example, modified polyphenylene ether (modified PPE) oligomers represented by the following formula (PPE-o) and having polymerizable functional groups at both ends.
  • modified PPE modified polyphenylene ether
  • X at both ends of formula (PPE-o) is independently a group represented by the following formula (x1) or (x2). In these formulas, "*" indicates a bond to the oxygen atom.
  • m is preferably 1 to 20, more preferably 3 to 15, and n is preferably 1 to 20, more preferably 3 to 15.
  • the curable compositions of the present disclosure may include one or more inorganic fillers (F) (fillers).
  • the inorganic filler (F) include silica such as spherical silica, metal oxides such as alumina, titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, Among them, from the viewpoint of low thermal expansion, silica, mica, talc, etc. are preferable, and spherical silica is more preferable.
  • the inorganic filler (F) may be an inorganic filler that has been surface-treated with a surface treatment agent having a polymerizable functional group.
  • the polymerizable functional group include a group having a polymerizable carbon-carbon unsaturated bond, an epoxy group, an isocyanate group, a hydroxy group, a mercapto group, an amino group, a ureido group, a carboxy group, a sulfonic acid group, an acid chloride group, and a chlorine atom.
  • Examples of the group having a polymerizable carbon-carbon unsaturated bond include a vinyl group, an allyl group, a dienyl group, a (meth)acryloyloxy group, and a (meth)acrylamino group.
  • the surface treatment agent examples include a silane coupling agent having a polymerizable functional group.
  • the inorganic filler (F) can be surface-treated with an epoxy silane type, vinyl silane type, methacryl silane type, or amino silane type silane coupling agent.
  • the timing of the surface treatment with the silane coupling agent is not particularly limited.
  • the inorganic filler (F) surface-treated with the silane coupling agent may be prepared in advance, or the silane coupling agent may be added by the integral blend method when preparing the curable composition.
  • the average particle size of the inorganic filler (F) is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 3 ⁇ m.
  • the "average particle size” refers to the median diameter ( D50 ) determined by measuring the particle size distribution using a laser analysis type particle size distribution analyzer.
  • the inorganic filler (F) can contribute to improving the dielectric properties, heat resistance, flame retardancy, and toughness of the cured product, as well as reducing the thermal expansion coefficient.
  • the thermoplastic elastomer (E), the crosslinking agent (C), and the polymerizable functional groups of the inorganic filler (F) can react when the curable composition is cured, and the crosslink density of the cured product can increase. This can contribute to improving the heat resistance of the cured product.
  • thermosetting composition described in Patent Document 1 listed in the section [Background Art] contains a large amount of an inorganic filler as one of its essential components, and preferably contains 30 parts by mass or more of the inorganic filler per 100 parts by mass of the ethylene-propylene-diene copolymer.
  • a large amount of inorganic filler is difficult to disperse well in the composition and is prone to agglomeration in the composition, making it difficult to prepare a uniform composition and difficult to apply the composition thinly and uniformly to the surfaces of various substrates.
  • thermosetting composition containing a large amount of an inorganic filler tends to have reduced adhesion to various substrates (substrate adhesion) and a high (i.e., deteriorated) dielectric tangent (D f ) under high frequency conditions.
  • the inorganic filler (F) can be well dispersed in the curable composition, and a uniform curable composition can be easily prepared.
  • a curable composition containing an appropriate amount of organic solvent (S) has a low solid content and a viscosity suitable for coating, and can be applied thinly and uniformly to the surface of various substrates. That is, a curable composition containing an appropriate amount of organic solvent (S) has good thin-wall coating properties.
  • the (semi-)cured product of the curable composition has a sufficiently low dielectric tangent ( Df ) under high frequency conditions and good adhesion to various substrates (substrate adhesion).
  • the content of the inorganic filler (F) in the curable composition of the present disclosure (the total amount when multiple types are used) is 0 to 25 parts by mass, preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, particularly preferably 0 to 10 parts by mass, and most preferably 0 to 5 parts by mass, and may be 0 part by mass, relative to 100 parts by mass in total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • the heat resistance of the cured product can be improved even if a small amount of inorganic filler (F) is used or no inorganic filler (F) is used.
  • the crosslinking reaction proceeds well and a crosslinked structure is sufficiently formed in the cured product by using a thermoplastic elastomer (E) having high crosslinking reactivity and an appropriate amount of a crosslinking agent (C) and a radical polymerization initiator (I), so that it is considered that the heat resistance of the cured product can be improved even without using an inorganic filler (F).
  • E thermoplastic elastomer
  • C crosslinking agent
  • I radical polymerization initiator
  • the curable composition of the present disclosure comprises one or more radical polymerization initiators (I).
  • the radical polymerization initiators (I) can accelerate the curing reaction of the curable composition.
  • an organic peroxide, an azo compound, or other known polymerization initiators can be used as the radical polymerization initiator (I).
  • dicumyl peroxide benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethyls
  • the content of the radical polymerization initiator (I) (in the case of a plurality of types) in the curable composition of the present disclosure is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and particularly preferably 0.1 to 1 part by mass, relative to 100 parts by mass in total of the thermoplastic elastomer (E) and the crosslinking agent (C).
  • the curable compositions of the present disclosure may optionally contain one or more additives, such as flame retardants, antioxidants, compatibilizers, defoamers, heat stabilizers, antistatic agents, UV absorbers, dyes, pigments, lubricants, and dispersants.
  • additives such as flame retardants, antioxidants, compatibilizers, defoamers, heat stabilizers, antistatic agents, UV absorbers, dyes, pigments, lubricants, and dispersants.
  • the curable composition of the present disclosure may contain one or more organic solvents (S) as necessary.
  • the organic solvent (S) is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene, and xylene; and chlorinated hydrocarbons such as trichloroethylene.
  • toluene alone or a mixed solvent containing 75% by mass or more of toluene is preferable because it has high solubility for the thermoplastic elastomer (E) and can be dried at a low temperature.
  • the timing of blending the organic solvent (S) is not particularly limited.
  • the organic solvent (S) may be blended when preparing a curable composition containing the thermoplastic elastomer (E), the crosslinking agent (C), the radical polymerization initiator (I), and, if necessary, the inorganic filler (F), or the organic solvent (S) may be blended after preparing a curable composition containing the thermoplastic elastomer (E), the crosslinking agent (C), the radical polymerization initiator (I), and, if necessary, the inorganic filler (F), before coating the composition on a substrate.
  • the curable composition of the present disclosure includes a curable composition that does not contain an organic solvent (S), a curable composition before the organic solvent (S) is blended, and a curable composition that contains an organic solvent (S).
  • the curable composition containing an appropriate amount of organic solvent (S) has a low solid content and a viscosity suitable for coating, and can be applied thinly and uniformly to the surface of various substrates. That is, the curable composition containing an appropriate amount of organic solvent (S) has good thin coatability.
  • the viscosity of the curable composition during coating is preferably 20 to 1000 mPa ⁇ s, more preferably 50 to 300 mPa ⁇ s, particularly preferably 50 to 200 mPa ⁇ s, and most preferably 50 to 150 mPa ⁇ s.
  • the solid content concentration of the curable composition at the time of coating is preferably 0.5 to 20 mass %, more preferably 2 to 10 mass %.
  • the method for drying the curable composition containing the organic solvent (S) is not particularly limited.
  • the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying, and heat drying is preferred.
  • the drying temperature of the heat drying is not particularly limited, and is preferably 40 to 100° C. from the viewpoint of not volatilizing the crosslinking agent (C) and selectively and efficiently volatilizing only the organic solvent (S) to obtain a dried product of the curable composition not containing the organic solvent (S).
  • metal foils with resin such as resin coated copper foil (RCC) have a relatively high tackiness when the resin layer is in an uncured, dry state (A stage), so it is common to semi-cure (B stage) the resin layer before winding it into a roll.
  • RCC resin coated copper foil
  • metal foils with resin such as RCC
  • the melt viscosity at the heat press temperature is relatively low, and there is a risk of it flowing due to pressure.
  • semi-cure (B stage) the resin layer beforehand before subjecting it to heat pressing it is common to semi-cure (B stage) the resin layer beforehand before subjecting it to heat pressing.
  • the reaction of the semi-cured (B stage) resin layer proceeds gradually even when stored at room temperature, so there are limitations on the storage period and/or storage environment temperature. For this reason, low-temperature storage (refrigerated storage or frozen storage) may be required.
  • the resin layer made of the dried product of the curable composition of the present disclosure has relatively low tackiness, so that the resin layer or a sheet-like laminate such as an RCC containing the resin layer can be wound into a roll without (semi-)curing or using a protective film.
  • Tackiness can be evaluated, for example, by overlaying a protective film on the resin layer made of the dried product of the curable composition and checking for the presence or absence of any migration from the resin layer to the protective film. If there is no migration from the resin layer, the dried product of the curable composition has low migration and can be said to have low tackiness.
  • the resin layer made of the dried product of the curable composition of the present disclosure has a relatively high melt viscosity at the heat press temperature even in an uncured dry state (A stage state). Therefore, even if the resin layer made of the dried product of the curable composition of the present disclosure is subjected to heat pressing in an uncured dry state (A stage state), flow due to pressure is suppressed.
  • the resin layer made of the dried product of the curable composition of the present disclosure or a sheet-like laminate such as an RCC containing the same can be stored for a normal period of time under normal environmental temperatures such as room temperature (20 to 25°C) when the resin layer is in an uncured dry state (A stage state) without using a protective film. In other words, the resin layer made of the dried product of the curable composition of the present disclosure or a sheet-like laminate such as an RCC containing the same does not require special consideration for the storage period and storage environmental temperature.
  • the resin layer made of the dried product of the curable composition of the present disclosure has a relatively high melt viscosity at high temperatures in an uncured, dry state (A-stage state). Therefore, in the case of a resin layer made of the dried product of the curable composition of the present disclosure or a sheet-like laminate such as an RCC that contains the resin layer, even when the resin layer is in an uncured, dry state (A-stage state), the flow of the resin caused by heat pressing is suppressed, and heat pressing can be performed well.
  • the curable composition of the present disclosure may be either thermosetting or active energy ray curable. For applications such as resin-attached metal foil, metal-clad laminate, and wiring board, thermosetting is preferred.
  • the curable composition of the present disclosure may be (semi-)cured, for example, at 100 to 300°C.
  • the curable composition of the present disclosure may be semi-cured, for example, at 100 to 180°C.
  • the curable composition of the present disclosure may be fully cured, for example, at 150 to 300°C.
  • the curable composition of the present disclosure may be semi-cured at 100 to 180°C, and then fully cured (fully cured) at 150 to 300°C.
  • thermoplastic elastomer (E) that does not contain polar atoms or has a small amount of polar atoms is used, and an appropriate amount of a crosslinking agent (C) having a heteroatom is used.
  • C crosslinking agent
  • a small amount of inorganic filler (F) can be used or no inorganic filler (F) can be used.
  • the cured product of the curable composition of the present disclosure is a resin with an effectively reduced dielectric loss tangent (D f ) under high frequency conditions.
  • the cured product of the curable composition of the present disclosure has a dielectric loss tangent ( Df ) at a frequency of 10 GHz of 0.0030 or less, preferably 0.0020 or less, more preferably 0.0018 or less, even more preferably 0.0016 or less, even more preferably 0.0014 or less, even more preferably 0.0010 or less, particularly preferably 0.0008 or less, and most preferably 0.0007 or less.
  • the lower limit of the dielectric loss tangent ( Df ) at a frequency of 10 GHz is not particularly limited, and is, for example, 0.0001.
  • the cured product of the curable composition of the present disclosure may have a dielectric loss tangent ( Df ) at a frequency of 28 GHz of 0.0030 or less, 0.0020 or less, 0.0018 or less, 0.0016 or less, 0.0014 or less, 0.0010 or less, 0.0008 or less, or 0.0007 or less.
  • the lower limit of the dielectric loss tangent ( Df ) at a frequency of 28 GHz is not particularly limited, and is, for example, 0.0001.
  • the "dielectric loss tangent ( Df )" is a value measured using a cavity resonator at a temperature of 23° C.
  • the dielectric loss tangent ( Df ) can be determined by the method described in the section [Examples] below.
  • the crosslinking reaction proceeds well by using the thermoplastic elastomer (E) having high crosslinking reactivity and the appropriate amount of the crosslinking agent (C) and the radical polymerization initiator (I), and a crosslinking structure is sufficiently formed in the cured product of the curable composition. Therefore, even if a small amount of the inorganic filler (F) is used or even if no inorganic filler (F) is used, the cured product of the curable composition of the present disclosure can have good heat resistance. Components are mounted on the surface of the wiring board using solder. In order to ensure the reliability of the wiring board when mounting the components, it is preferable that the resin contained in the wiring board has good heat resistance.
  • the cured product of the curable composition of the present disclosure can have good heat resistance against a solder bath of 260°C or more or 280°C or more.
  • a crosslinked structure is sufficiently formed between the substrates and the resin layer, so that the resin layer made of the cured product of the curable composition of the present disclosure can have good substrate adhesion to various substrates.
  • the resin layer made of the cured product of the curable composition of the present disclosure has good substrate adhesion to both substrates and can function as an adhesive layer that bonds the two substrates.
  • the curable composition of the present disclosure is suitable for use as a resin layer contained in a metal-clad laminate in which a resin layer and a metal foil are sequentially laminated on at least one surface of a core substrate, or as a resin layer contained in a wiring board in which a resin layer and wiring are sequentially laminated on at least one surface of a core substrate.
  • the resin sheet of the present disclosure is made of a dried product, semi-cured product, or cured product of the curable composition of the present disclosure.
  • 1 shows a schematic cross-sectional view of a resin sheet according to an embodiment of the present disclosure, in which reference numeral 1 denotes a resin sheet.
  • the method for producing the resin sheet of the present disclosure is not particularly limited.
  • Examples of the production method include a method in which the curable composition of the present disclosure containing an organic solvent (S) is applied onto a release sheet such as a polytetrafluoroethylene (PTFE) sheet to form a coating film, and the coating film is dried, semi-cured or cured, and the release sheet is peeled off.
  • S organic solvent
  • PTFE polytetrafluoroethylene
  • a resin sheet made of a cured product of the curable composition of the present disclosure has an effectively reduced dielectric tangent (D f ) under high frequency conditions, good heat resistance, and good adhesion to substrates, and can be used for various applications.
  • a resin sheet made of a dried or semi-cured product of the curable composition of the present disclosure can be overlaid on various substrates, and the resin sheet is cured by heating and pressurizing to produce a laminate including the substrate and a resin layer made of the cured product of the curable composition of the present disclosure.
  • the resin layer made of the cured product of the curable composition of the present disclosure has effectively reduced dielectric tangent ( Df ) under high frequency conditions, has good heat resistance, and has good adhesion to substrates.
  • the thickness of the resin sheet of the present disclosure is represented by t [ ⁇ m], and in the curable composition, the amount of the crosslinking agent (C) per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C) is represented by q [parts by mass].
  • the thickness (t) of the resin sheet is designed depending on the application, and can be, for example, 0.1 to 50 ⁇ m for applications such as resin-coated metal foil, metal-clad laminate, and wiring board. It is preferable that t ⁇ q [ ⁇ m parts by mass] is 40 or less. t ⁇ q [ ⁇ m parts by mass] is preferably 35 or less, more preferably 30 or less, and particularly preferably 25 or less.
  • the lower limit of t ⁇ q [ ⁇ m parts by mass] is not particularly limited, and can be, for example, 1, 3, 5, or 7. If t ⁇ q [ ⁇ m/mass parts] is equal to or less than the upper limit, the tackiness of the resin sheet in an uncured dry state (A-stage state) is low, and curling of the resin sheet is effectively suppressed, which is preferable. For example, after the resin sheet is wound into a roll, a flat resin sheet without curling can be smoothly unwound from the roll. Furthermore, when t ⁇ q [ ⁇ m ⁇ parts by mass] is equal to or less than the upper limit, bleeding out of the crosslinking agent (C) from the resin sheet can be effectively suppressed, which is preferable.
  • a resin sheet made of a dried product, semi-cured product, or cured product of the curable composition of the present disclosure preferably has t [ ⁇ m] of 0.1 to 50 and t ⁇ q [ ⁇ m/parts by mass] of 40 or less.
  • the laminate of the present disclosure includes a substrate and a resin layer made of a dried product, semi-cured product, or cured product of the curable composition of the present disclosure.
  • the substrate is not particularly limited, and examples thereof include a fiber substrate, a resin substrate, a metal substrate, and a composite substrate thereof.
  • FIG. 2 shows a schematic cross-sectional view of a laminate according to one embodiment of the present disclosure.
  • the laminate 2 of this embodiment is a laminate with a two-layer structure in which a resin layer 22 is laminated on one surface of a substrate 21. It may also be a three-layer structure in which a resin layer 22 is formed on both sides of a substrate 21, a three-layer structure in which a resin layer 22 is sandwiched between two substrates 21, or a four-layer or more laminate structure including one or more substrates 21 and one or more resin layers 22.
  • the constituent fibers of the fiber substrate are not particularly limited, and include inorganic fibers such as glass fibers, silica fibers, and carbon fibers; organic fibers such as aramid fibers and polyester fibers; and combinations thereof.
  • inorganic fibers such as glass fibers, silica fibers, and carbon fibers
  • organic fibers such as aramid fibers and polyester fibers
  • glass fibers are preferred.
  • the form of the glass fiber substrate include glass cloth, glass paper, and glass mat.
  • the constituent resin of the resin substrate is not particularly limited, and examples thereof include polyimide, polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer, polyether sulfide, and combinations thereof.
  • the form of the resin substrate may be a resin sheet or the like.
  • the constituent metal of the metal substrate copper, silver, gold, aluminum, and combinations thereof are preferred because they have low electrical resistance.
  • the form of the metal substrate may be metal foil, etc. Copper foil is preferred for applications such as resin-coated metal foil, metal-clad laminate, and wiring board.
  • the substrate may be a prepreg including a fiber substrate and a (semi-)cured product of a curable composition including one or more known curable polymers.
  • the curable polymer include modified polyphenylene ether (modified PPE) oligomers represented by the above formula (PPE-o) and having polymerizable functional groups at both ends, divinyl aromatic polymers, and aliphatic hydrocarbon compounds having crosslinkable functional groups.
  • the curable composition may contain one or more known additives such as a flame retardant, an inorganic filler, and an antioxidant, as necessary.
  • the prepreg can be produced by impregnating a fiber substrate with a curable composition containing one or more known curable polymers and (semi-)curing the composition by heat curing, etc.
  • the prepreg can be a known or commercially available product.
  • the method for producing the laminate of the present disclosure is not particularly limited. Examples include a method of applying the curable composition of the present disclosure containing an organic solvent (S) onto at least one surface of a substrate, drying or semi-curing as necessary, and then curing; a method of overlaying the resin sheet of the present disclosure, which is made of the dried or semi-cured product of the curable composition of the present disclosure, onto at least one surface of a substrate, and heating and pressurizing the resin sheet to cure it.
  • S organic solvent
  • a resin layer made of a cured product of the curable composition of the present disclosure has effectively reduced dielectric tangent ( Df ) under high frequency conditions, good heat resistance, and good adhesion to substrates.
  • a laminate of the present disclosure including this resin layer has effectively reduced dielectric tangent ( Df ) under high frequency conditions, good heat resistance, and good interlayer adhesion, and can be used for various applications.
  • One embodiment of the laminate of the present disclosure is a resin-coated metal foil that includes a metal foil and a resin layer made of a dried product, semi-cured product, or cured product of the curable composition of the present disclosure.
  • a resin-coated metal foil that uses copper foil as the metal foil is called a resin-coated copper foil (RCC).
  • the thickness of the resin layer is t [ ⁇ m], and the amount of the crosslinking agent (C) in the curable composition per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C) is q [parts by mass].
  • the thickness (t) of the resin layer is designed depending on the application, and can be, for example, 0.1 to 50 ⁇ m for applications such as resin-coated metal foils, metal-clad laminates, and wiring boards. It is preferable that t ⁇ q [ ⁇ m parts by mass] is 40 or less. t ⁇ q [ ⁇ m parts by mass] is preferably 35 or less, more preferably 30 or less, and particularly preferably 25 or less.
  • the lower limit of t ⁇ q [ ⁇ m parts by mass] is not particularly limited, and can be, for example, 1, 3, 5, or 7. If t ⁇ q [ ⁇ m/parts by mass] is equal to or less than the upper limit, the tackiness of the resin layer in an uncured dry state (A-stage state) is low, and curling of the laminate such as the resin-coated metal foil is effectively suppressed, which is preferable. For example, after the laminate such as the resin-coated metal foil is wound into a roll, a flat laminate such as the resin-coated metal foil without curling can be smoothly unwound from the roll.
  • t ⁇ q [ ⁇ m/parts by mass] is equal to or less than the upper limit, bleeding out of the crosslinking agent (C) from the resin layer can be effectively suppressed, which is preferable.
  • the resin-coated metal foil is wound into a roll, material transfer to the exposed metal surface of the metal foil (the surface on which the resin layer is not laminated) can be effectively suppressed.
  • the preferred ranges of t and t ⁇ q [ ⁇ m/parts by mass] of the resin layer in an uncured dry state (A-stage state) after (semi-)curing are also the same as above. That is, the resin layer made of the dried product, semi-cured product, or cured product of the curable composition of the present disclosure preferably has t [ ⁇ m] of 0.1 to 50 and t ⁇ q [ ⁇ m/parts by mass] of 40 or less.
  • the metal-clad laminate of the present disclosure has a core substrate and a metal foil laminated on at least one surface of the core substrate, and has a resin layer between the core substrate and the metal foil, the resin layer being made of a cured product of the curable composition of the present disclosure.
  • the metal foil copper foil, silver foil, gold foil, aluminum foil, and combinations thereof are preferred due to their low electrical resistance, and copper foil is more preferred.
  • the metal foil may have a metal plating layer on the surface.
  • the metal foil may be a carrier-attached metal foil including an ultra-thin metal foil and a carrier metal foil supporting the ultra-thin metal foil.
  • the metal foil may have a surface treatment such as an anti-rust treatment, a silane treatment, a roughening treatment, and a barrier formation treatment on at least one surface.
  • the thickness of the metal foil is not particularly limited, and is preferably 0.1 to 100 ⁇ m, more preferably 0.2 to 50 ⁇ m, and particularly preferably 1.0 to 40 ⁇ m, since it is suitable for forming a conductor pattern (also called a circuit pattern) such as wiring.
  • the metal-clad laminate may be a single-sided metal-clad laminate having metal foil on one side, or a double-sided metal-clad laminate having metal foil on both sides, with a double-sided metal-clad laminate being preferred.
  • the single-sided metal-clad laminate can be produced by stacking one or more of the above prepregs and a metal foil, and then heating and pressing the resulting first temporary laminate.
  • the double-sided metal-clad laminate can be produced by sandwiching one or more of the above prepregs between a pair of metal foils and applying heat and pressure to the resulting first temporary laminate.
  • a metal-clad laminate using copper foil as the metal foil is called a copper clad laminate (CCL).
  • the core substrate is preferably made of a prepreg that has been heated and pressed.
  • the prepreg contains a fiber substrate and a resin, and may contain one or more additives such as an inorganic filler and a flame retardant, if necessary.
  • the dielectric loss tangent ( Df ) of the core substrate at a frequency of 10 GHz is not particularly limited, but is preferably 0.0030 or less, more preferably 0.0020 or less.
  • the lower limit of the dielectric loss tangent ( Df ) at a frequency of 10 GHz is not particularly limited, but is, for example, 0.0001.
  • the dielectric loss tangent ( Df ) of the core substrate at a frequency of 28 GHz is not particularly limited, but is preferably 0.0030 or less, more preferably 0.0020 or less.
  • the lower limit of the dielectric loss tangent ( Df ) at a frequency of 28 GHz is not particularly limited, but is, for example, 0.0001.
  • the conditions for heating and pressing the first temporary laminate are not particularly limited, and are preferably, for example, a temperature of 170 to 250° C., a pressure of 0.3 to 30 MPa, and a time of 3 to 240 minutes.
  • the metal-clad laminate 3A shown in FIG. 3A is a single-sided metal-clad laminate (laminate) in which a resin layer 32 made of a cured product of the curable composition of the present disclosure and a metal foil (metal layer) 33 are sequentially laminated on one side of a core substrate 31 made of a heated and pressurized prepreg.
  • 3B is a double-sided metal-clad laminate in which a resin layer 32 made of a cured product of the curable composition of the present disclosure and a metal foil (metal layer) 33 are sequentially laminated on both sides of a core substrate 31 made of a heated and pressurized prepreg.
  • the resin layer 32 made of the cured product of the curable composition of the present disclosure can function as an adhesive layer that enhances the adhesion between the core substrate 31 and the metal foil (metal layer) 33 .
  • the metal-clad laminates 3A and 3B may have layers other than those described above.
  • the thickness of the core substrate can be designed appropriately depending on the application. From the viewpoint of preventing breakage of the wiring board, it is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and particularly preferably 100 ⁇ m or more. From the viewpoint of flexibility, miniaturization, and weight reduction of the wiring board, it is preferably 300 ⁇ m or less, more preferably 250 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
  • a resin layer formed from a cured product of the curable composition of the present disclosure has effectively reduced dielectric tangent (D f ) under high frequency conditions, good heat resistance, and good adhesion to substrates.
  • the metal-clad laminate of the present disclosure containing the resin layer effectively reduces the dielectric loss tangent (D f ) under high frequency conditions, and is suitable for use as a wiring board.
  • the metal-clad laminate of the present disclosure including the resin layer has good heat resistance, and can have good heat resistance to a solder bath of 260° C. or higher or 280° C. or higher.
  • the metal-clad laminate of the present disclosure including the resin layer has good interlayer adhesion, good metal foil adhesion, and good metal foil peel strength.
  • the metal foil may be a metal foil having a roughened surface (roughened metal foil) or a metal foil having a non-roughened surface (non-roughened metal foil).
  • a roughened metal foil is used, the adhesion of the metal foil can be improved, but a loss of high frequency current is likely to occur.
  • the resin layer made of the cured product of the curable composition of the present disclosure has good adhesion to the substrate. Therefore, even if a low-roughness roughened metal foil or a non-roughened metal foil having a small surface roughness is used as the metal foil, the resin layer made of the cured product of the curable composition of the present disclosure is interposed between the core substrate and the metal foil, thereby improving the adhesion of the metal foil and increasing the metal foil peel strength.
  • the ten-point average roughness (R zjis ) of the surface of the resin layer side of the low-roughness-roughened metal foil and the non-roughened metal foil may be 1.5 ⁇ m or less or 1.0 ⁇ m or less.
  • the lower limit is not particularly limited, and is, for example, 0.1 ⁇ m.
  • the "ten-point average roughness (R zjis ) of the surface" can be measured in accordance with JIS B 0601.
  • the wiring board of the present disclosure includes an insulating layer containing a cured product of the curable composition of the present disclosure, and wiring.
  • the wiring board can be manufactured by forming a conductor pattern (circuit pattern) such as wiring using the metal foil on the outermost surface of the metal-clad laminate of the present disclosure.
  • Methods for forming the conductor pattern such as wiring include a subtractive method in which the metal foil is etched to form wiring, and a modified semi-additive process (MSAP) method in which wiring is formed on the metal foil by plating.
  • FIG. 4 A schematic cross-sectional view of a wiring board according to an embodiment of the present disclosure is shown in Fig. 4.
  • the wiring board 4 is formed by forming a conductor pattern (circuit pattern) 34 such as wiring 34W using a metal foil (metal layer) 33 on at least one outermost surface of the metal-clad laminate 3B of the second embodiment shown in Fig. 3B.
  • the wiring board 4 has a conductor pattern (circuit pattern) 34 such as wiring 34W formed on at least one surface of a core substrate 31 made of heated and pressurized prepreg.
  • a multilayer wiring board may be manufactured by further stacking one or more prepregs on the obtained wiring board, sandwiching the resultant prepreg between a pair of metal foils, heating and pressing the obtained second provisional laminate, and forming a conductor pattern such as wiring using the metal foil on the outermost surface.
  • the metal foil on the outermost surface may be disposed on only one side of the second provisional laminate.
  • the wiring board of the present disclosure is suitable for use in a high frequency range (a range of frequencies of 1 GHz or more).
  • the present disclosure it is possible to provide a curable composition that reduces the content of inorganic filler, effectively reduces the dielectric tangent ( Df ) under high frequency conditions, and can provide a resin that has good heat resistance and good adhesion to substrates.
  • the curable composition of the present disclosure is suitable for applications such as resin-coated metal foils, metal-clad laminates, and wiring boards, but can be used for any application.
  • the curable composition of the present disclosure is suitable for applications such as resin-coated metal foils, metal-clad laminates, and wiring boards.
  • INDUSTRIAL APPLICABILITY The resin-coated metal foil and metal-clad laminate of the present disclosure are suitable for wiring boards and the like used in various electric devices and various electronic devices.
  • the wiring board of the present disclosure is suitable for portable electronic devices such as mobile phones, smartphones, personal digital assistants, and notebook computers; antennas for mobile phone base stations and automobiles; electronic devices such as servers, routers, and backplanes; wireless infrastructure; radar for collision prevention, etc.; various sensors (e.g., automotive sensors such as engine management sensors), and the like.
  • the wiring board of the present disclosure is particularly suitable for applications in which communication is performed using high-frequency signals, and is suitable for various applications in which reduced transmission loss is required in the high-frequency range.
  • Examples 1-1 to 1-4, 2-1 to 2-5, 3-1 to 3-4, 4-1 to 4-3, 5-1 to 5-2, 6-1 to 6-3, 7-1 to 7-3, and 8 to 17 are working examples, and 101 to 109 are comparative examples. Unless otherwise specified, operations were carried out at room temperature of about 25°C.
  • EC Comparative Thermoplastic Elastomer
  • EC-1 Hydrogenated poly(styrene)-poly(isoprene-co-butadiene)-poly(styrene) triblock copolymer (A-B-A type triblock copolymer), "Septon 4055" manufactured by Kuraray Co., Ltd., weight average molecular weight (Mw): about 350,000, ratio of total mass of polymer block (A) to mass of polymer block (B) ((A)/(B) mass ratio): 30/70.
  • Mw weight average molecular weight
  • ⁇ Inorganic filler (F)> F-1) Spherical silica surface-treated with a vinylsilane type silane coupling agent, "SC2300-SVJ” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m.
  • Pre-1 AGC prepreg "Meteorwave 8000" (a composite material including a glass fiber substrate and a cured product of a curable composition including a modified polyphenylene ether (modified PPE) oligomer represented by the above formula (PPE-o) and a silica filler), dielectric dissipation factor (D f ) at a frequency of 10 GHz: 0.0016.
  • modified PPE modified polyphenylene ether
  • D f dielectric dissipation factor
  • PTFE sheet (PTFE-1) Polytetrafluoroethylene (PTFE) sheet manufactured by Aram Co., Ltd., thickness 100 ⁇ m.
  • the weight average molecular weight (Mw) of the thermoplastic elastomer was determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the GPC device used was a Tosoh Corporation "HLC-8320GPC” equipped with a differential refractive index detector (RI detector). Tetrahydrofuran was used as the eluent.
  • the columns used were "TSKgel SuperHZ2000”, “TSKgel SuperHZ2500”, “TSKgel SuperHZ3000” and “TSKgel SuperHZ4000” (all manufactured by Tosoh Corporation) connected in series.
  • a sample solution was prepared by dissolving 20 mg of resin in 2 mL of tetrahydrofuran. 10 ⁇ l of the sample solution was injected to measure the chromatogram. GPC was performed using 10 standard polystyrene points with molecular weights in the range of 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was created. The Mw was determined based on this calibration curve.
  • a curable composition (varnish) having a solid content adjusted to an appropriate concentration using toluene was applied onto a copper foil by a roll-to-roll process, and then dried.
  • a curable composition (varnish) having a solid content adjusted to an appropriate concentration was applied by a die coating method onto the roughened surface of a copper foil (Cu-1) continuously unwound from a copper foil roll to form a coating film.
  • the resulting coating film/copper foil laminate was then heated in four stages using four hot air heating ovens.
  • the heating conditions in each heating oven were as follows: First heating oven from the upstream side: 35°C for 2 minutes, Second upstream furnace: 50°C for 2 minutes; The third furnace from the upstream side: 50°C for 2 minutes, Fourth furnace from the upstream: 50°C for 2 minutes.
  • a laminate resin-coated copper foil, RCC
  • the thickness of the resin layer was 2 ⁇ m.
  • the thickness of the resin layer was the thickness shown in the table (3 ⁇ m, 6 ⁇ m, 8 ⁇ m, or 10 ⁇ m).
  • the thickness of the resin layer was adjusted by adjusting the solid content concentration, the conveying speed of the copper foil, the thickness of the shim plate included in the die, and the distance between the die and the copper foil.
  • the solid content concentration of the curable composition (varnish) was adjusted to 5.0 mass%. Evaluation was performed according to the following criteria.
  • the curable composition (varnish) was stably and uniformly applied onto the copper foil, and a resin layer of the designed thickness was stably and satisfactorily formed.
  • the curable composition (varnish) could not be uniformly applied onto the copper foil, and a resin layer of the designed thickness could not be satisfactorily formed.
  • Example 101 Appearance of dried product (presence or absence of cloudiness and/or streaks)
  • a curable composition Varnish adjusted to a solid content concentration of 6.0 mass% using toluene was applied to one surface of a copper foil (Cu-1) (length 200 mm, width 200 mm) using an applicator with a coating gap of 100 ⁇ m to form a coating film with a wet thickness of 100 ⁇ m.
  • the obtained copper foil with the coating film was placed in an oven set at 80° C. and heated for 1 minute in an air atmosphere to obtain a laminate (resin-coated copper foil, RCC) of the copper foil and a resin layer (6 ⁇ m thick) made of a dried product of the curable composition.
  • the resin layer of the obtained laminate was visually observed to confirm the presence or absence of white turbidity and/or streaks.
  • a polyethylene terephthalate (PET) film having a thickness of 25 ⁇ m and having one side subjected to a sandblasting treatment was prepared.
  • the above protective film was placed on the resin layer of the laminate (copper foil with resin, RCC) after the evaluation of the above "appearance of the dried product" so that the resin layer and the blasted surface of the protective film were in contact with each other.
  • RCC copper foil with resin
  • MVLP300 vacuum diaphragm laminator
  • vacuum lamination was performed under conditions of lamination temperature 25°C, pressing force 0.2 MPa, and pressing time 60 seconds to obtain a laminated sheet with a protective film.
  • the protective film was peeled off from the obtained laminated sheet with a protective film, and the blasted surface was visually observed to confirm the presence or absence of migration from the resin layer.
  • Copper foil (Cu-1) (200 mm long, 200 mm wide) was placed on the resin layer of the laminate (resin-coated copper foil, RCC) obtained as described above, so that the resin layer and the non-roughened surface of the copper foil (Cu-1) were in contact with each other.
  • RCC resin-coated copper foil
  • the resin-coated copper foil (RCC) was peeled off from the copper foil (Cu-1) laminated later by hand at a peel angle of approximately 90° and a peel speed of approximately 200 mm/min. After peeling from the copper foil (Cu-1), the resin-coated copper foil (RCC) was visually inspected to see if it curled.
  • the dielectric loss tangent (D f ) of a resin sheet made of a cured product of the curable composition was measured at a temperature of 23° C. and a frequency of 10 GHz by a cavity resonance method.
  • a curable composition (varnish) having a solid content concentration adjusted to 7.5% by mass using toluene was applied to an area of one surface of a PTFE sheet (PTFE-1) (length 150 mm, width 150 mm) excluding the peripheral portion (area within about 30 mm from each side) using an applicator with a coating gap of 400 ⁇ m, to form a coating film with a wet thickness of 400 ⁇ m.
  • the obtained PTFE sheet with the coating film was placed in an oven set at 80° C. and heated in an air atmosphere for 1 minute to obtain a laminated sheet of the PTFE sheet and a resin layer (30 ⁇ m thick) made of the dried product of the curable composition. Two such laminated sheets were prepared.
  • the two laminated sheets thus obtained were stacked so that the resin layers faced each other to obtain a provisional laminate.
  • a spacer having a height of 50 ⁇ m for adjusting the thickness was disposed between the peripheral edge of one laminated sheet and the peripheral edge of the other laminated sheet.
  • the obtained provisional laminate was vacuum-pressed under a surface pressure of 2.0 MPa, and heated according to a heating profile in which the temperature was increased from room temperature to 215°C at a temperature increase rate of 3°C/min, held at 215°C for 120 minutes, and then decreased to room temperature at a temperature decrease rate of 7°C/min, thereby curing the dried product of the curable composition.
  • the PTFE sheets on both sides of the obtained laminate were peeled off to obtain a resin sheet (50 ⁇ m thick) made of a cured product of the curable composition.
  • a test piece measuring 70 mm square was cut out from the obtained resin sheet, and the test piece was heated for 2 hours in an oven set at 120° C. The test piece was taken out of the oven and left to stand for 16 hours in an environment of 25° C./relative humidity 50 ⁇ 5%, and then the dielectric loss tangent (D f ) of the test piece was measured in an environment of 23° C./relative humidity 50 ⁇ 5%.
  • a network analyzer (“ZNB40" manufactured by Rohde & Schwarz) and a cavity resonator for 10 GHz (“Cavity Resonator S Series" manufactured by AET Corporation) were used.
  • Example 101 solder heat resistance of double-sided copper-clad laminate (CCL)
  • a curable composition in which the solid content concentration was adjusted to an appropriate concentration using toluene was applied to one surface of a copper foil (Cu-1) (length 200 mm, width 200 mm) using an applicator to form a coating film.
  • the obtained copper foil with the coating film was placed in an oven set at 80°C and heated for 1 minute in an air atmosphere to obtain a laminate (resin-coated copper foil, RCC) of the copper foil and a resin layer made of a dried product of the curable composition. Two sheets of this laminate (resin-coated copper foil, RCC) were prepared.
  • the two laminates (resin-coated copper foil, RCC) were laminated with the resin layers facing each other via two prepregs (Pre-1) (length 150 mm, width 150 mm) to obtain a provisional laminate.
  • the provisional laminate was heated from room temperature to 215° C. at a heating rate of 3° C./min while vacuum pressing under a surface pressure of 2.0 MPa, held at 215° C. for 120 minutes, and cooled to room temperature at a heating rate of 7° C./min, thereby curing the dried product of the curable composition.
  • a double-sided copper-clad laminate double-sided CCL
  • each resin layer was 6 ⁇ m.
  • the thickness of each resin layer was the thickness shown in the table (3 ⁇ m, 6 ⁇ m, 8 ⁇ m, or 10 ⁇ m).
  • the thickness of the resin layer was adjusted by the solid content concentration of the curable composition (varnish) and the coating gap of the applicator. For example, when forming a 6 ⁇ m-thick resin layer, the solid content concentration of the curable composition (varnish) was adjusted to 6.0 mass %, and the coating gap of the applicator was set to 100 ⁇ m.
  • Example 101 two copper foils (Cu-1) (200 mm long, 200 mm wide) were stacked with two prepregs (Pre-1) (150 mm long, 150 mm wide) in between to obtain a temporary laminate.
  • This temporary laminate was pressurized and heated in the same manner as in the other examples to obtain a double-sided copper-clad laminate (double-sided CCL) in which the core substrate and each copper foil were directly stacked.
  • the stacking was performed so that the roughened surface of each copper foil was in contact with the core substrate.
  • a 100 mm square test piece was cut from the double-sided copper-clad laminate (double-sided CCL) obtained in each example, and this test piece was immersed in a solder bath at 288°C for 600 seconds. The test piece removed from the solder bath was visually observed to check for the presence or absence of appearance defects such as blistering, peeling, or whitening. In each example, a total of 10 samples were evaluated, and the number of samples (n) that did not experience appearance defects was determined, and the solder heat resistance data was expressed as n/10.
  • Example 101 Copper foil peel strength of double-sided copper clad laminate (CCL)
  • a curable composition in which the solid content concentration was adjusted to an appropriate concentration using toluene was applied to one surface of a copper foil (Cu-1) (length 200 mm, width 200 mm) using an applicator to form a coating film.
  • the obtained copper foil with the coating film was placed in an oven set at 80°C and heated for 1 minute in an air atmosphere to obtain a laminate (resin-coated copper foil, RCC) of the copper foil and a resin layer made of a dried product of the curable composition. Two sheets of this laminate (resin-coated copper foil, RCC) were prepared.
  • the two laminates (resin-coated copper foil, RCC) were laminated with two prepregs (Pre-1) (length 150 mm, width 150 mm) in between so that the resin layers faced each other to obtain a provisional laminate.
  • the provisional laminate was heated from room temperature to 215° C. at a heating rate of 3° C./min while vacuum pressing under a surface pressure of 2.0 MPa, held at 215° C. for 120 minutes, and cooled to room temperature at a heating rate of 7° C./min, thereby curing the dried product of the curable composition.
  • a double-sided copper-clad laminate double-sided CCL
  • the thickness of each resin layer was set to two conditions, 2 ⁇ m and 6 ⁇ m.
  • the thickness of each resin layer was set to the thickness shown in the table (3 ⁇ m, 6 ⁇ m, 8 ⁇ m, or 10 ⁇ m).
  • the thickness of the resin layer was adjusted by the solid content concentration of the curable composition (varnish) and the coating gap of the applicator. For example, when forming a resin layer with a thickness of 2 ⁇ m, the solid content concentration of the curable composition (varnish) was adjusted to 4.0 mass %, and the coating gap of the applicator was set to 50 ⁇ m. For example, when forming a resin layer with a thickness of 6 ⁇ m, the solid content concentration of the curable composition (varnish) was adjusted to 6.0 mass %, and the coating gap of the applicator was set to 100 ⁇ m.
  • Example 101 two copper foils (Cu-1) (200 mm long, 200 mm wide) were stacked with two prepregs (Pre-1) (150 mm long, 150 mm wide) in between to obtain a temporary laminate.
  • This temporary laminate was pressurized and heated in the same manner as in the other examples to obtain a double-sided copper-clad laminate (double-sided CCL) in which the core substrate and each copper foil were directly stacked.
  • the stacking was performed so that the roughened surface of each copper foil was in contact with the core substrate.
  • a plurality of materials having the composition shown in Tables 1 to 6 were mixed with toluene as an organic solvent (S) to prepare a curable composition (varnish) having a solid content concentration of 4.0 to 7.5 mass%, and subjected to various evaluations.
  • the solid content concentration was adjusted by the amount of toluene, and the solid content concentration was adjusted according to the evaluation items.
  • the evaluation results are shown in Tables 1 to 6. Conditions not shown in the tables were common conditions.
  • the unit of the blending amount in the table is “parts by mass” unless otherwise specified.
  • the unit of the blending amount of the radical polymerization initiator (I) is "phr” which is the added amount “parts by mass” per 100 parts by mass of the total of the thermoplastic elastomer (E) or (EC) and the crosslinking agent (C) or (CC).
  • Example 101 In Example 101, no curable composition was prepared, and two copper foils (Cu-1) were laminated with two prepregs (Pre-1) therebetween, and the laminate was pressurized and heated to obtain a double-sided copper-clad laminate, which was then evaluated. In this example, the lamination was performed so that the roughened surface of each copper foil was in contact with the core substrate. The evaluation results are shown in Table 6.
  • thermoplastic elastomers (E) selected from the group consisting of block copolymers comprising one or more polymer blocks (A) consisting of structural units derived from one or more aromatic vinyl compounds including one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, and one or more polymer blocks (B) consisting of structural units derived from one or more conjugated diene compounds, and hydrogenated products of the block copolymers; 2.5 to 30 parts by mass of a crosslinking agent (C) having a hetero atom per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C); 0 to 25 parts by mass of an inorganic filler (F) relative to 100 parts by mass in total of the thermoplastic elastomers (A) consisting of structural units derived from one or more aromatic vinyl compounds including one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, and one or more polymer blocks (B
  • a cured product was obtained in which the dielectric tangent (D f ) under high frequency conditions was effectively reduced.
  • the dielectric tangent (D f ) at a frequency of 10 GHz of the cured products in Examples 1 to 17 was 0.0030 or less, 0.0020 or less, 0.0018 or less, and 0.0016 or less, and in some examples, it was 0.0014 or less, 0.0010 or less, 0.0008 or less, or 0.0007 or less.
  • a double-sided copper-clad laminate was obtained having a cured film made of the cured product of the curable composition between the core substrate and each copper foil. All of the obtained double-sided copper-clad laminates had good solder heat resistance and copper foil peel strength (substrate adhesion). It is believed that the use of a thermoplastic elastomer (E) with high crosslinking reactivity and an appropriate amount of a crosslinking agent (C) and a radical polymerization initiator (I) allowed the crosslinking reaction to proceed smoothly, and sufficient crosslinking structures were formed in the resin layer made of the cured product, between the core substrate and the resin layer, and between the resin layer and the copper foil.
  • the crosslinking agent (C) having a heteroatom used in these examples had good compatibility with the thermoplastic elastomer (E), so the effect of improving the solder heat resistance of the cured product could be stably obtained.
  • the thickness of the resin layer is t [ ⁇ m], and the amount of the crosslinking agent (C) in the curable composition per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C) is q [parts by mass].
  • t [ ⁇ m] was 0.1 to 50, and t ⁇ q [ ⁇ m/parts by mass] was not more than 40.
  • Examples 2-2 to 2-5 in which the thickness of the resin layer was changed with the same composition as in Example 2-1, in the resin-coated copper foils (RCC) containing a resin layer made of a dried product of a curable composition obtained in Examples 2-2 to 2-4 in which t [ ⁇ m] was 0.1 to 50 and t ⁇ q [ ⁇ m parts by mass] was 40 or less, a copper foil was laminated on the resin layer using a vacuum laminator, and no curling was observed even after the laminated copper foil was peeled off.
  • RRCC resin-coated copper foils
  • Example 101 no curable composition was prepared, and copper foil was directly laminated to both sides of a core substrate, with the roughened surface of the copper foil in contact with the core substrate, to obtain a double-sided copper-clad laminate.
  • the resulting double-sided copper-clad laminate had poor copper foil peel strength (substrate adhesion).
  • Examples 102 and 103 which used a comparative crosslinking agent (CC) that did not have a heteroatom, the compatibility between the crosslinking agent (CC) and the thermoplastic elastomer (E) was not very good, so the resin layer made of the dried curable composition had a poor appearance and the effect of improving the solder heat resistance of the cured product was unstable.
  • CC crosslinking agent
  • E thermoplastic elastomer
  • Example 104 in which a comparative thermoplastic elastomer (EC) was used that did not have a structural unit derived from one or more alkylstyrene compounds having an alkyl group having 1 to 8 carbon atoms, the resulting double-sided copper-clad laminate had poor solder heat resistance and copper foil peel strength (substrate adhesion).
  • the comparative thermoplastic elastomer (EC) has a low crosslinking reactivity, and therefore it is considered that a crosslinked structure was not sufficiently formed within the resin layer consisting of the cured product, between the core substrate and the resin layer, and between the resin layer and the copper foil.
  • Example 105 in which no crosslinking agent (C) was used, and in Example 106, in which the amount of crosslinking agent (C) was less than 2.5 parts by mass per 100 parts by mass of the total of the thermoplastic elastomer (E) and the crosslinking agent (C), the obtained double-sided copper-clad laminate had poor or unstable solder heat resistance. It is believed that the crosslinking reaction did not proceed well, and a sufficient crosslinked structure was not formed in the resin layer made of the cured product, between the core substrate and the resin layer, and between the resin layer and the copper foil.
  • Example 107 in which no radical polymerization initiator (I) was used, the resulting double-sided copper-clad laminate had poor solder heat resistance and copper foil peel strength (substrate adhesion). It is believed that the crosslinking reaction did not proceed well, and a crosslinked structure was not sufficiently formed within the resin layer made of the cured product, between the core substrate and the resin layer, and between the resin layer and the copper foil.
  • Example 108 in which the amount of the crosslinking agent (C) was more than 30 parts by mass relative to the total of 100 parts by mass of the thermoplastic elastomer (E) and the crosslinking agent (C), the viscosity of the curable composition (varnish) with a solid content concentration of 5.0% by mass was low, and the thin-wall coating properties were poor.
  • the obtained double-sided copper-clad laminate had poor copper foil peel strength (substrate adhesion). It is considered that the crosslink density of the cured product became too high, impairing the flexibility of the resin layer, and the resin layer became easily broken during the evaluation of the peel strength.
  • the amount of heteroatoms contained in the cured product was large, so that the dielectric loss tangent (D f ) of the cured product at a frequency of 10 GHz was as high as 0.005.
  • Example 109 in which 50 parts by mass of inorganic filler (F) was used per 100 parts by mass of the total of thermoplastic elastomer (E) and crosslinking agent (C), the thin coating properties of the curable composition (varnish) with a solids concentration of 5.0% by mass were poor, and the copper foil peel strength (substrate adhesion) of the obtained double-sided copper-clad laminate was poor. It is believed that aggregates of inorganic filler (F) were formed in the curable composition. It is also believed that the large amount of inorganic filler (F) made the resin layer made of the cured product brittle.

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  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition durcissable permettant de donner une résine pour laquelle une tangente de perte diélectrique (Df) dans des conditions de haute fréquence est efficacement réduite et qui présente une bonne résistance à la chaleur et une bonne adhérence au substrat. La composition durcissable comprend un ou plusieurs élastomères thermoplastiques (E) choisis dans le groupe constitué de copolymères séquencés comprenant chacun un bloc polymère (A) constitué de motifs structuraux dérivés d'un ou plusieurs composés vinyliques aromatiques comprenant un composé (alkyl en C1-C8)styrène et un bloc polymère (B) constitué de motifs structuraux dérivés d'un ou plusieurs composés diènes conjugués et des produits d'hydrogénation des copolymères séquencés ; de 2,5 à 30 parties en masse d'un agent de réticulation contenant un hétéroatome (C) et de 0 à 25 parties en masse d'une charge inorganique (F) pour 100 parties en masse de la somme des élastomères thermoplastiques (E) et de l'agent de réticulation (C) ; et un initiateur de polymérisation radicalaire (I). L'objet durci obtenu à partir de celui-ci présente une tangente de perte diélectrique (Df), telle que mesurée à une température de 23°C et une fréquence de 10 GHz, inférieure ou égale à 0,0030.
PCT/JP2023/046231 2023-02-01 2023-12-22 Composition durcissable, feuille de résine, objet multicouche, stratifié revêtu de métal et carte de câblage Ceased WO2024161859A1 (fr)

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JP2023-013768 2023-02-01
JP2023013768 2023-02-01
JP2023103166 2023-06-23
JP2023-103166 2023-06-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025187615A1 (fr) * 2024-03-08 2025-09-12 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié plaqué de feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257296A (ja) * 2005-03-17 2006-09-28 Kuraray Co Ltd 伸縮性部材
WO2018159080A1 (fr) * 2017-03-02 2018-09-07 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique, et carte de câblage
WO2021010432A1 (fr) * 2019-07-17 2021-01-21 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié métallisé et carte de câblage
WO2022059625A1 (fr) * 2020-09-18 2022-03-24 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné l'utilisant, film pourvu de résine, feuille métallique pourvue de résine, stratifié revêtu de métal et panneau de câblage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006257296A (ja) * 2005-03-17 2006-09-28 Kuraray Co Ltd 伸縮性部材
WO2018159080A1 (fr) * 2017-03-02 2018-09-07 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film revêtu de résine, feuille métallique revêtue de résine, stratifié à revêtement métallique, et carte de câblage
WO2021010432A1 (fr) * 2019-07-17 2021-01-21 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié métallisé et carte de câblage
WO2022059625A1 (fr) * 2020-09-18 2022-03-24 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné l'utilisant, film pourvu de résine, feuille métallique pourvue de résine, stratifié revêtu de métal et panneau de câblage

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025187615A1 (fr) * 2024-03-08 2025-09-12 三菱瓦斯化学株式会社 Composition de résine, produit durci, préimprégné, stratifié plaqué de feuille métallique, feuille composite de résine, carte de circuit imprimé et dispositif à semi-conducteur

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