Classifications

• • 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
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • 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
  • C08K5/49—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
• • 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

• the present invention is based on a curable resin composition having excellent dielectric properties and flame retardancy, a film composed of a curable resin composition, a cured product obtained by curing the curable resin composition, and a curable resin composition.
• the present invention relates to a prepreg made of a material, a metal-clad laminate, and a printed wiring board.
• thermosetting resins such as phenol resin, epoxy resin, and polyimide resin have been used for printed wiring boards. Although these resins have various performances in a well-balanced manner, they have insufficient dielectric properties in the high frequency region.
• Patent Document 1 a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound and an ethyl vinyl aromatic compound, and specific at both ends are specified.
• a curable resin composition comprising a polyphenylene ether oligomer having a vinyl group is disclosed.
• the resin composition used as a molding material for a substrate material or the like generally contains a halogen-based flame retardant such as a bromine-based flame retardant or a halogen such as a halogen-containing epoxy resin such as tetrabromobisphenol A type epoxy resin. In many cases, the contained compound was blended.
• a resin composition containing such a halogen-containing compound contains halogen in its cured product, and may generate harmful substances such as hydrogen halide during combustion, so that the human body and the natural environment It has been pointed out that there is a concern that it will have an adverse effect on.
• molding materials such as substrate materials are required to be halogen-free, so-called halogen-free.
• the present invention has been made in view of such a situation, and provides a novel curable resin composition which is excellent in dielectric properties and flame retardancy and can give a halogen-free cured resin or molded product. With the goal.
• Another object of the present invention is to provide a film, a cured product, a prepreg, a metal-clad laminate, and a printed wiring board obtained from this curable resin composition.
• the present invention is a polyfunctional vinyl aromatic copolymer containing (A) a repeating unit (a1) derived from a divinyl aromatic compound and a repeating unit (a2) derived from a monovinyl aromatic compound, wherein the repeating unit is described above.
• the repeating unit (a1) is contained in an amount of 2 mol% or more and less than 95 mol%
• the repeating unit (a2) is contained in an amount of 5 mol% or more and 98 mol%. It contains less than 2 to 80 mol% of a repeating unit (a1-1) having an unsaturated group represented by the following formula (a1-1).
• R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.
• the number average molecular weight is 300 to 100,000, the molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight is 100.0 or less, and it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
• the phosphorus-containing compound (B) contains two or more 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO) groups.
• DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
• the compound is one or more selected from the phosphorus-containing compounds represented by the following formulas (b1-1), (b1-2) and (b1-3).
• a in the formula represents a hydrocarbon group having 1 to 10 carbon atoms
• m1, m2, m3 and m4 are repetition numbers and independently represent integers of 0 to 6, respectively
• n1, n2 and n3 are. It is the number of substitutions and independently indicates an integer of 0 to 4
• R indicates a hydrocarbon group having 1 to 6 carbon atoms.
• the phosphorus-containing compound (B) is a phosphorus-containing compound represented by the following formula (b2).
• n4, n5 and n6 in the formula are independently 0 or 1
• X and Z are independently O or S, respectively.
• the dashed line represents either with or without a bond.
• R 2 to R 7 independently represent any of an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a sulfur-containing substituent.
• the phosphorus-containing compound (B) is a phosphorus-containing compound represented by the following formula (b3).
• Y in the formula represents an arylene group having 6 to 12 carbon atoms, a cycloalkyne group having 3 to 12 carbon atoms, a cycloalkyne group having 6 to 12 carbon atoms, a methylene group or an alkylene group having 2 to 12 carbon atoms.
• R 8 and R 9 independently represent hydrogen, alkoxy group, alkyl group, aryl group, or silyl group, respectively
• R 10 and R 11 independently represent hydrogen, hydroxy group, or alkyl having 1 to 6 carbon atoms, respectively. Indicates a group.
• the phosphorus-containing compound (B) is a vinyl group-containing DOPO compound, a vinyl group-containing diphenylphosphine compound, a vinyl group-containing phosphazene compound, a vinyl group-containing phosphoric acid ester compound, and an acrylic group-containing DOPO compound. It is preferable that the phosphorus-containing vinyl compound (b5) selected from the above group is one kind or two or more kinds.
• the curable resin composition of the present invention is preferably a (b6) phosphorus-containing olefin polymer in which the (B) phosphorus-containing compound is composed of (b4) a cycloolefin compound and (b5) a phosphorus-containing vinyl compound.
• the (b4) cycloolefin compound is one or more selected from the cycloolefins represented by the groups of the following formulas (b4-1), (b4-2) and (b4-3). Is preferable.
• m5 in the equation indicates an integer of 1 to 10.
• the phosphorus-containing olefin polymer (b6) can be obtained by polymerizing (b4) a cycloolefin compound and (b5) a phosphorus-containing vinyl compound using a polymerization catalyst.
• the polymerization catalyst can be selected from either a peroxide, a ruthenium-containing catalyst, or a metallocene catalyst.
• the phosphorus-containing vinyl compound is a phosphorus-containing compound selected from the group of a vinyl group-containing DOPO compound, a vinyl group-containing diphenylphosphine compound, a vinyl group-containing phosphazene compound, a vinyl group-containing phosphoric acid ester compound, and an acrylic group-containing DOPO compound. It is preferable that there is one kind or two or more kinds.
• the phosphorus-containing compound (B) may be a vinyl group-containing DOPO compound represented by the following formulas (b5-1), (b5-2) or (b5-3). ..
• n9 in the equation indicates an integer of 1 to 4
• Q indicates -CH 2- or -CH 2- O-CH 2-
• c indicates an integer of 1 to 4
• d indicates an integer of 0 to 4. Indicates an integer of 6.
• the phosphorus-containing compound (B) may be a vinyl group-containing diphenylphosphine compound represented by the following formula (b5-4).
• the phosphorus-containing compound (B) may be a vinyl group-containing phosphazene compound containing a group represented by the following formula (b5-5) or (b5-6).
• n10 and n11 in the equation independently represent integers of 3 to 10.
• the phosphorus-containing compound (B) may be a vinyl group-containing phosphoric acid ester compound represented by the following formula (b5-7) or (b5-8).
• the phosphorus-containing compound (B) may be an acrylic group-containing DOPO compound represented by the following formula (b5-9).
• the phosphorus-containing compound (b1-1) may be a phosphorus-containing compound represented by the following formula (b1-11). However, at least one of R and R'is not hydrogen, but a functional group selected from the group of the following formula (b1-11A), and A is represented by a single bond, a methylene group, or the following formula (b1-11B). It is selected from divalent aromatic hydrocarbon groups consisting of groups of Here, R 12 and R 13 are alkyl groups having 1 to 3 carbon atoms, n12 and n13 are independently integers of 0 to 4, and X is a structure represented by the following formula (b1-11BX). one of.
• the curable resin composition of the present invention contains (A) a soluble polyfunctional vinyl aromatic copolymer, (B) a phosphorus-containing compound, (C) a radical polymerization initiator, and, if necessary, (D) a filler.
• the present invention is a cured product obtained by curing the above-mentioned curable resin composition, a film composed of the curable resin composition, or a curable composite material composed of the curable resin composition and a base material. It may be.
• the content of the base material is preferably in the range of 5 to 90% by weight.
• the present invention may be a cured composite material obtained by curing the curable composite material, or a laminate having a layer of the cured composite material and a metal foil layer, and the curable resin. It may be a metal foil with a resin having a film of the composition on one side or both sides of the metal foil, or a varnish for a circuit board material obtained by dissolving the curable resin composition in an organic solvent.
• the curable resin composition of the present invention contains (A) a soluble polyfunctional vinyl aromatic copolymer and (B) a phosphorus-containing compound as essential components, and particularly preferably (C) a radical polymerization initiator, ( D) Further contains a filler.
• (A) to (D) are also referred to as components (A) to (D), respectively.
• the component (A) is a polyfunctional vinyl aromatic copolymer containing a repeating unit (a1) derived from a divinyl aromatic compound and a repeating unit (a2) derived from a monovinyl aromatic compound.
• the repeating unit (a1) is contained in an amount of 2 mol% or more and less than 95 mol%
• the repeating unit (a2) is contained in an amount of 5 mol% or more and 98. It contains less than mol% and contains 2 to 80 mol% of a repeating unit (a1-1) having an unsaturated group represented by the above formula (a1-1).
• Mn is 300 to 100,000
• the molecular weight distribution is 100.0 or less, and it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
• the polyfunctional vinyl aromatic copolymer contains, for example, a repeating unit (a1) derived from a divinyl aromatic compound represented by the following formula and a structural unit derived from a repeating unit (a2) derived from a monovinyl aromatic compound.
• a repeating unit (a1-1) having an unsaturated group represented by the following formula is included as an essential component.
• These structural units may be arranged regularly or randomly.
• R 14 is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a monovinyl aromatic compound
• R 1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a divinyl aromatic compound.
• R 1 and R 14 in the above formula are aromatic hydrocarbon groups selected from the group consisting of a phenyl group, a biphenyl group, a naphthalene group, and a terphenyl group, and these fragrances. Each group hydrocarbon group may have a substituent.
• the repeating unit referred to in the present specification is derived from the monomer of the raw material, and is present in the main chain of the copolymer and appears repeatedly, and a unit or a terminal group existing in the terminal or side chain. including.
• the repeating unit is also called a structural unit.
• the terminal group referred to in the present specification includes not only the terminal group derived from the above-mentioned monomer but also the terminal group derived from the chain transfer agent described later.
• the structural unit (a1) derived from the divinyl aromatic compound is preferably contained in an amount of 2 mol% or more and less than 95 mol% with respect to the total of the structural unit (a2) derived from the divinyl aromatic compound and the monovinyl aromatic compound. It is preferably 10 to 70 mol%, more preferably 15 to 65 mol%. Further, the structural unit (a2) may be contained in an amount of 5 mol% or more and less than 98 mol%, preferably 10 to 90 mol%, and more preferably 15 to 85 mol%. If the structural unit (a2) is less than 5 mol%, the molding processability is insufficient, and if it exceeds 98 mol%, the heat resistance of the cured product is insufficient.
• the structural unit (a1) derived from the divinyl aromatic mixture can have a plurality of structures such as one in which only one of the two vinyl groups has reacted and one in which two have reacted. Of these, the above formula (a1-).
• the repeating unit (a1-1) in which only one vinyl group represented by 1) has reacted is 2 to 80 mol%, preferably 5 to 60 mol%, based on the total of the structural units (a1) and (a2). , More preferably 10 to 50 mol%, particularly preferably 15 to 40 mol%. Within this range, the dielectric loss tangent is low, the toughness is high, the heat resistance is excellent, and the compatibility with other resins is excellent.
• the vinyl group present in the structural unit (a1-1) acts as a cross-linking component and contributes to the development of heat resistance of the polyfunctional vinyl aromatic copolymer.
• the structural unit (a2) derived from the monovinyl aromatic compound does not have a vinyl group because it is usually considered that the polymerization proceeds by the addition reaction of 1, 2 of the vinyl group.
• the structural unit (a2) does not act as a cross-linking component, but contributes to the development of moldability.
• Styrene or ethyl vinylbenzene is preferably used as the monovinyl aromatic compound, but other monovinyl aromatic compounds can also be used.
• the content of the structural unit derived from styrene or ethyl vinylbenzene is preferably 50 mol% or more of the structural unit (a2).
• Ethyl vinylbenzene includes o-form, m-form, p-form or a mixture of these positional isomers.
• Examples of monovinyl aromatic compounds other than the above include vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; nuclear alkyl substitutions such as o-methylstyrene, m-methylstyrene, p-methylstyrene and o, p-dimethylstyrene. Vinyl aromatic compounds; and the like.
• ethyl vinyl biphenyl each position isomer or each position isomer or
• ethyl vinyl biphenyl is preferable because it prevents gelation of the soluble polyfunctional vinyl aromatic copolymer, is solvent-soluble, has a high effect of improving processability, is low in cost, and is easily available. (Contains a mixture of these), or ethylvinylnaphthalene (including each position isomer or a mixture thereof).
• the Mn (number average molecular weight of standard polystyrene equivalent measured using GPC) of the polyfunctional vinyl aromatic copolymer is 300 to 100,000, preferably 400 to 80,000, and more preferably 500 to 30,000. , More preferably 500 to 8,000.
• Mn is less than 300, the amount of the monofunctional copolymer component contained in the soluble polyfunctional vinyl aromatic copolymer increases, so that the heat resistance of the cured product tends to decrease, and Mn is 100. If it exceeds 000, gel is likely to be formed and the viscosity is increased, so that the molding processability tends to be lowered.
• the value of the molecular weight distribution (Mw / Mn) is 100.0 or less, preferably 50.0 or less, more preferably 30.0 or less, and most preferably 20.0. If it exceeds 100.0, the processing characteristics of the soluble polyfunctional vinyl aromatic copolymer tend to deteriorate, and gel tends to be generated.
• the polyfunctional vinyl aromatic copolymer is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform as a solvent, but is preferably soluble in any of the above solvents.
• solvent-soluble and polyfunctional copolymer it is necessary that a part of the vinyl group of divinylbenzene remains without cross-linking and has an appropriate degree of cross-linking.
• "soluble in a solvent” means that 5 g or more of a soluble polyfunctional vinyl aromatic copolymer is dissolved in 100 g of the above solvent, more preferably 30 g or more, and particularly preferably 50 g or more. It is to be.
• divinyl aromatic compound and the monovinyl aromatic compound in addition to the divinyl aromatic compound and the monovinyl aromatic compound, other monomer components such as a trivinyl aromatic compound, a trivinyl aliphatic compound, a divinyl aliphatic compound, and a monovinyl aliphatic compound can be used as long as the effects of the present invention are not impaired.
• One or two or more kinds can be used, and the structural unit (a5) derived from these other monomer components can be introduced into the polyfunctional vinyl aromatic copolymer.
• Examples of the other monomer components include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, and 1 , 4-Butandiol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triallyl isocyanurate, norbornene and the like. These can be used alone or in combination of two or more.
• the molar fraction with respect to the total of all the monomer components is less than 30 mol%. That is, it is preferable that the mole fraction is less than 30 mol% with respect to the total of the structural units (a1), (a2) and (a5).
• the polyfunctional vinyl aromatic copolymer is obtained by polymerizing a monomer containing a divinyl aromatic compound and a monovinyl aromatic compound in the presence of a Lewis acid catalyst.
• the Lewis acid catalyst used in the polymerization is a compound composed of a metal ion (acid) and a ligand (base), and can be used without particular limitation as long as it can receive an electron pair.
• metal fluoride or a complex thereof is preferable from the viewpoint of thermal decomposition resistance of the obtained copolymer, and in particular, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti.
• ether complex of boron trifluoride examples include diethyl ether and dimethyl ether.
• chain transfer agent can be added at the time of polymerization for the purpose of controlling the molecular weight.
• R is a hydrogen atom or a monovalent substituent.
• substituent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms are used. be.
• the alkyl group, alkenyl group, and alkynyl group referred to in the present specification may be linear or branched.
• CTR represents a chain transfer agent.
• the chain transfer agent chemically modifies the ends of the copolymer, it also serves as a compound that plays a role in introducing terminal groups that enable the addition of functions such as toughness, low dielectric property, and adhesion.
• Examples of such a compound having a function as a chain transfer agent include an alcohol compound, a mercaptan compound, a carboxylic acid compound, a carboxylic acid anhydride compound, an ether compound, a thioether compound, an ester compound, and a thioester compound. ..
• a monomer having low homopolymerization property can also be used as a molecular weight modifier.
• a monomer having low homopolymerization property include a cycloolefin compound.
• cycloolefin compounds include monocyclic cyclic olefins such as cyclobutene, cyclopentene, and cyclooctene, as well as compounds having a norbornene ring structure such as norbornene and dicyclopentadiene (hereinafter referred to as norbornene compounds) and inden.
• the phosphorus-containing compound as the component (B) will be described.
• the phosphorus-containing compound (B) is selected from compounds having any of the structures represented by the above formulas.
• the phosphorus-containing compound represented by the formulas (b1-1), (b1-2) or (b1-3) is a phosphorus-containing compound containing a DOPO group in its structure, and as a specific example, the following formula (b1-) Examples thereof include compounds represented by the structures shown in 11) to (b1-19).
• the phosphorus-containing compound represented by the formula (b2) is a phosphorus-containing compound containing a DOPO group or a diphenylphosphine oxide group in the structure, and specific examples thereof are the following formulas (b2-11) to (b2-13). Examples thereof include compounds represented by the structure shown in.
• the phosphorus-containing compound represented by the formula (b3) is a phosphorus-containing compound containing an alkylphosphine oxide group in its structure, and has a structure according to any of the following formulas (b3-11) to (b3-24).
• the phosphorus-containing compound (B) may be a phosphorus-containing olefin polymer composed of (b4) a cycloolefin compound and (b5) a phosphorus-containing vinyl compound.
• the cycloolefin compound of (b4) is one or more selected from the cycloolefins represented by the above formulas (b4-1), (b4-2) and (b4-3), and as a specific example, Examples thereof include 5-vinyl-2-norbornene, dicyclopentadiene, and cycloolefins having a structure represented by the following formulas (b4-11) to (b4-12).
• the phosphorus-containing vinyl compound is not particularly limited as long as it has a phosphorus atom and a vinyl group in its structure. Specific examples include phosphorus-containing vinyl compounds represented by the above formulas (b5-1) to (b5-9).
• the catalyst for polymerizing the phosphorus-containing olefin polymer described above is any one of a peroxide, a ruthenium-containing catalyst, and a metallocene catalyst.
• ruthenium-containing catalysts especially Grubbs catalysts
• Specific examples of the Grubbs catalyst include a compound having a structure represented by the following formula (2), or (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinilidene) dichloro (o-phenylethylene).
• phosphorus-containing compound (B) one or more selected from the phosphorus-containing vinyl compounds represented by the above formulas (b5-1) to (b5-9) are not used in combination with (b4) cycloolefin. , May be used alone.
• the blending ratio of the (A) polyfunctional vinyl aromatic copolymer and the (B) phosphorus-containing compound is 10 parts by weight of the (A) component and 10 parts of the (B) component. It is often contained in the range of to 100 parts by weight, preferably 30 to 90 parts by weight, and more preferably 40 to 80 parts by weight. With such a content, the curable resin composition is more excellent in heat resistance and flame retardancy of the cured product while maintaining the excellent dielectric properties of the curable resin composition of the present invention. It is considered that this is because the flame retardant can be sufficiently enhanced while sufficiently suppressing the deterioration of the dielectric property and the heat resistance of the cured product due to the inclusion of the flame retardant.
• the curable resin composition of the present invention has a dielectric constant (Dk) of 3.5 or less, preferably 3.0 or less, and a dielectric loss tangent (Df) of 0.006 or less, preferably 0.005 even after curing. It is as follows.
• the flame retardancy also shows performance of V-1 or higher in the UL standard.
• the peak temperature of tan ⁇ in the dynamic viscoelasticity measurement (DMA, tensile test method) is 200 ° C. or higher, and the 90 ° peel strength of the cured product of the thermosetting resin composition with respect to the copper foil is 0.5 kN / m or higher. Is preferable.
• the curable resin composition of the present invention can contain a radical polymerization initiator (also referred to as a radical polymerization catalyst) as the component (C).
• a radical polymerization initiator also referred to as a radical polymerization catalyst
• the curable resin composition of the present invention is cured by causing a cross-linking reaction by means such as heating as described later, but the reaction temperature at that time is lowered or cross-linking of unsaturated groups is performed.
• a radical polymerization initiator is contained for the purpose of accelerating the reaction.
• (C) A known substance is used as the radical polymerization initiator. Typical examples are benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy).
• Hexin-3 di-t-butyl peroxide, t-butyl cumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis There are peroxides such as (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilyl peroxide.
• peroxides such as (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (
• 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator.
• ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene is preferably used.
• ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene has a relatively high reaction start temperature. Therefore, it is possible to suppress the acceleration of the curing reaction at a time when it is not necessary to cure, such as when the prepreg is dried, and it is possible to suppress the deterioration of the storage stability of the curable resin composition of the present invention.
• ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene has low volatility, so that it does not volatilize during prepreg drying or storage, and has good stability.
• the radical polymerization initiator may be used alone or in combination of two or more.
• the amount of the radical polymerization initiator blended is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, still more preferably 100 parts by weight, based on 100 parts by weight of the (A) polyfunctional vinyl aromatic copolymer. 0.5 to 5 parts by weight. Within this range, the reaction proceeds satisfactorily without inhibiting the curing reaction.
• the curable resin composition of the present invention can contain a filler as the component (D).
• a filler examples include those added to enhance heat resistance and flame retardancy of the cured product of the curable resin composition, and known fillers can be used, but are not particularly limited. Further, by containing a filler, heat resistance, dimensional stability, flame retardancy and the like can be further improved. Specifically, silica such as spherical silica, alumina, titanium oxide, metal oxides such as mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. And so on.
• silica, mica, and talc are preferable, and spherical silica is more preferable. Further, one of these types may be used alone, or two or more types may be used in combination.
• the filler may be used as it is, or may be surface-treated with a silane coupling agent such as an epoxy silane type or an amino silane type.
• a silane coupling agent such as an epoxy silane type or an amino silane type.
• a vinylsilane type, a methacryloxysilane type, an acryloxysilane type, and a styrylsilane type silane coupling agent are preferable from the viewpoint of reactivity with a radical polymerization initiator.
• the adhesive strength with the metal foil and the interlayer adhesive strength between the resins are increased.
• the above-mentioned silane coupling agent may be added and used by the integral blend method.
• the content of the filler (D) is preferably in the range of 15 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the (A) polyfunctional vinyl aromatic copolymer.
• the curable resin composition of the present invention may contain a curable reactive resin, a thermoplastic resin, or both as components other than the above.
• the curable reaction type resin examples include known thermosetting resins and resins or compounds that copolymerize with a soluble polyfunctional vinyl aromatic copolymer to give a cured resin.
• vinyl ester resin polyvinyl benzyl resin, unsaturated polyester resin, curable vinyl resin, maleimide resin, epoxy resin, polycyanate resin, phenol resin, one type having one or more polymerizable unsaturated hydrocarbon groups in the molecule.
• vinyl compounds and the like can be mentioned.
• Preferable examples include polyvinylbenzyl resin, epoxy resin, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. Particularly preferred are polyvinylbenzyl resins and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule.
• the curable reactive resin is an epoxy resin
• it is preferably one or more epoxy resins selected from epoxy resins having two or more epoxy groups in one molecule.
• epoxy resins include cresol novolac type epoxy resins, triphenylmethane type epoxy resins, biphenyl epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins. These may be used alone or in combination of two or more.
• the curable resin composition of the present invention preferably does not contain a halogenated epoxy resin, but may be blended as necessary as long as the effects of the present invention are not impaired. By using such an epoxy resin, the influence on the excellent dielectric properties and fluidity of the curable resin composition of the present invention can be minimized, and the heat resistance and adhesion of the cured product can be sufficiently enhanced. it is conceivable that.
• the curable reactive resin is one or more vinyl compounds (hereinafter, also referred to as vinyl compounds) having one or more polymerizable unsaturated hydrocarbon groups in the molecule
• the type is not particularly limited. .. That is, the vinyl compounds may be those that can be cured by forming crosslinks by reacting with the polyfunctional vinyl aromatic copolymer of the present invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.
• the component (B) is excluded from these vinyl compounds.
• the vinyl compounds have a Mw of preferably 100 to 5,000, more preferably 100 to 4,000, and even more preferably 100 to 3,000. If Mw is less than 100, it may easily volatilize from the compounding component system of the curable resin composition. On the other hand, if Mw exceeds 5,000, the viscosity of the varnish of the curable resin composition and the melt viscosity at the time of heat molding may become too high. Therefore, when it is within the above range of Mw, a curable resin composition having excellent heat resistance of the cured product can be obtained. It is considered that this is because the crosslinks can be suitably formed by the reaction between the soluble polyfunctional vinyl aromatic copolymer and the vinyl compounds.
• Mw is a value measured using GPC.
• the average number of carbon-carbon unsaturated double bonds per molecule of vinyl compounds as a curable reactive resin is Although it depends on the Mw of the vinyl compounds, for example, it is preferably 1 to 20 and more preferably 2 to 18. If the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. Further, if the number of terminal double bonds is too large, the reactivity becomes too high, for example, the storage stability of the curable resin composition is lowered, the fluidity of the curable resin composition is lowered, and the like. Problems may occur.
• the vinyl compounds include PPE whose terminal is modified with a vinyl group, a styryl group, a methacryl group, etc., a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), and many having two or more methacryl groups in the molecule.
• Functional methacrylate compounds polyfunctional acrylate compounds having two or more acrylic groups in the molecule, vinyl compounds having two or more vinyl groups in the molecule (polyfunctional vinyl compounds) such as polybutadiene, and vinylbenzyl groups in the molecule.
• examples thereof include vinylbenzyl compounds such as styrene and divinylbenzene having the above. Among these, those having two or more carbon-carbon double bonds in the molecule are preferable.
• crosslinks are more preferably formed by the curing reaction, and the heat resistance of the cured product of the curable resin composition can be further enhanced. Further, these may be used alone or in combination of two or more. Further, a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination. Examples of the compound having one carbon-carbon unsaturated double bond in the molecule include a compound having one vinyl group in the molecule (monovinyl compound).
• thermoplastic resin examples include polystyrene, polyphenylene ether resin, polyetherimide resin, polyether sulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin and the like, and known thermoplastic elastomers such as styrene-. Ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.
• rubbers such as polybutadiene and polyisoprene can be mentioned.
• a polyphenylene ether resin (unmodified) and a hydrogenated styrene-butadiene copolymer can be mentioned.
• the total blending amount of the curable resin component and the thermoplastic resin component is preferably 1 to 60 parts by weight, more preferably 2 to 40 parts by weight, based on 100 parts by weight of the entire resin composition. .. It is particularly preferably 5 to 30 parts by weight.
• the curable resin composition of the present invention may further contain additives other than the above.
• additives include dispersion of defoamers such as silicone-based defoamers and acrylic acid ester-based defoamers, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and wet dispersants. Agents and the like can be mentioned.
• the curable resin composition of the present invention can be made into a cured product by heat curing, photocuring, or the like. Further, a film can be formed by a coating method or the like. It can also be a curable composite material such as a prepreg.
• a prepreg When manufacturing a prepreg, it is prepared in the form of a varnish for the purpose of impregnating the base material (fibrous base material) for forming the prepreg or for the purpose of using it as a circuit board material for forming the circuit board, and then using a resin varnish. It is good to do.
• the resin varnish is obtained by dissolving or dispersing a resin composition containing the above components (A) to (D) as essential components in a solvent.
• This resin varnish is suitable for circuit boards and can be used as a varnish for circuit board materials.
• Specific examples of the use of the circuit board material referred to here include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.
• the above resin varnish is prepared, for example, as follows. First, each component that can be dissolved in an organic solvent such as the components (A) to (D) and the curable reactive resin is put into the organic solvent and dissolved. At this time, if necessary, it may be heated. Then, if necessary, a component that does not dissolve in an organic solvent such as an inorganic filler is added and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like to obtain a varnish-like curable resin composition. Is prepared.
• the organic solvent used here is not particularly limited as long as it dissolves the components (A) to (D) and does not inhibit the curing reaction.
• ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; polar solvents such as dimethylacetamide and dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene. It is also possible to use one kind or a mixture of two or more kinds of these. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.
• the amount of the organic solvent used in preparing the resin varnish is preferably 5 to 900 parts by weight, more preferably 10 to 700 parts by weight, particularly preferably 10 parts by weight, based on 100 parts by weight of the curable resin composition of the present invention. Is 20 to 500 parts by weight.
• the curable resin composition of the present invention is an organic solvent solution such as a resin varnish, the amount of the organic solvent is not included in the calculation of the composition.
• the cured product obtained by curing the curable resin composition of the present invention can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film.
• the cured product of the semiconductor encapsulant material is a cast product or a molded product, and as a method for obtaining a cured product for such an application, a curable resin composition is cast, a transfer molding machine, an injection molding machine, or the like.
• a cured product can be obtained by molding using the product and further heating it at 80 to 230 ° C. for 0.5 to 10 hours.
• the cured product of the circuit board varnish is a laminate, and as a method for obtaining this cured product, the circuit board varnish is used as a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper. It can be obtained by impregnating and heat-drying to obtain a prepreg, which can be obtained by hot press molding alone or by laminating it with a metal foil such as a copper foil.
• an inorganic high-dielectric powder such as barium titanate or an inorganic magnetic material such as ferrite
• a curable resin composition or a resin varnish By blending an inorganic high-dielectric powder such as barium titanate or an inorganic magnetic material such as ferrite in a curable resin composition or a resin varnish, it is more excellent as a material for electronic parts, especially a material for high-frequency electronic parts. It becomes.
• the curable resin composition of the present invention can be used by laminating with a metal foil (meaning including a metal plate; the same applies hereinafter) as in the case of the cured composite material described later.
• a substrate is added to the curable composite material according to the curable resin composition of the present invention in order to increase mechanical strength and dimensional stability.
• Known materials are used as such a base material, and for example, various glass cloths such as roving cloths, cloths, chopped mats, and surfaced mats, asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths.
• Woven fabrics or non-woven fabrics obtained from liquid crystal fibers such as total aromatic polyamide fibers, total aromatic polyester fibers, polybenzozar fibers, woven fabrics or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Natural fiber cloth such as cotton cloth, linen cloth, felt, carbon fiber cloth, kraft paper, cotton paper, cloth such as natural cellulose cloth such as paper-glass mixed fiber paper, paper, etc. are used individually or in two or more types. It is also used.
• the proportion of the base material in the curable composite material is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight. If the amount of the base material is less than 5% by weight, the dimensional stability and strength of the composite material after curing are insufficient, and if the amount of the base material is more than 90% by weight, the dielectric properties of the composite material are inferior, which is not preferable.
• a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the base material, if necessary.
• general agents such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used.
• the curable resin composition of the present invention As a method for producing the curable composite material of the present invention, for example, the curable resin composition of the present invention and, if necessary, other components are placed in the above-mentioned aromatic, ketone or the like solvent or a mixed solvent thereof.
• examples thereof include a method in which the substrate is uniformly dissolved or dispersed, impregnated into the substrate, and then dried. Impregnation is performed by dipping, coating, or the like. The impregnation can be repeated a plurality of times as needed, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust to the desired resin composition and amount. It is possible.
• a cured composite material can be obtained by curing the curable composite material of the present invention by a method such as heating.
• the manufacturing method is not particularly limited, and for example, a plurality of curable composite materials can be superposed, and the layers can be bonded to each other under heat and pressure, and at the same time, thermosetting can be performed to obtain a cured composite material having a desired thickness. can. It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material once adhesively cured and the curable composite material.
• Laminate molding and curing are usually performed at the same time using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by laminating and molding in advance can be cured by heat treatment or another method.
• Curing, molding and curing of the curable resin composition or curable composite material of the present invention preferably takes place in a temperature range of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm 2 , and a time range of 1 minute to 10 hours.
• the temperature is 150 to 250 ° C.
• the pressure is 1 to 500 kg / cm 2
• the time is 1 minute to 5 hours.
• the laminate of the present invention is composed of a layer of the cured composite material of the present invention and a layer of metal foil.
• the metal foil used here include copper foil and aluminum foil.
• the thickness is not particularly limited, but is in the range of 3 to 200 ⁇ m, more preferably 3 to 105 ⁇ m.
• the curable resin composition of the present invention As a method for producing the laminate of the present invention, for example, the curable resin composition of the present invention described above, the curable composite material obtained from the base material, and a metal foil are laminated in a layer structure according to the purpose. Examples thereof include a method of adhering each layer under heat and pressure and at the same time thermosetting.
• the cured composite material and the metal foil are laminated in an arbitrary layer structure.
• the metal foil can be used as both a surface layer and an intermediate layer. In addition to the above, it is also possible to repeat lamination and curing a plurality of times to form multiple layers.
• Adhesive can also be used for adhesion to metal foil.
• the adhesive include, but are not limited to, epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives.
• the above-mentioned lamination molding and curing can be performed under the same conditions as the production of the cured composite material of the present invention.
• the curable resin composition of the present invention By molding the curable resin composition of the present invention into a film, it can be made into a film which is a form of the curable resin composition of the present invention.
• the thickness is not particularly limited, but is preferably in the range of 3 to 200 ⁇ m, more preferably 5 to 105 ⁇ m.
• the method for producing the film of the present invention is not particularly limited, and for example, the curable resin composition is uniformly dissolved or dispersed in a solvent such as an aromatic or ketone solvent or a mixed solvent thereof, and the PET film is produced. Examples thereof include a method of applying to a resin film such as, and then drying.
• the coating can be repeated a plurality of times as needed, and at this time, the coating can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and amount can be adjusted. Is.
• the resin-containing metal foil of the present invention is composed of the curable resin composition of the present invention and the metal foil.
• the metal foil used here include copper foil and aluminum foil.
• the thickness is not particularly limited, but is preferably in the range of 3 to 200 ⁇ m, more preferably 5 to 100 ⁇ m.
• the method for producing the metal foil with resin of the present invention is not particularly limited, and for example, the curable resin composition is uniformly dissolved or dispersed in a solvent such as an aromatic or ketone solvent or a mixed solvent thereof.
• the coating can be repeated a plurality of times as needed, and at this time, the coating can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust to the desired resin composition and amount. It is possible.
• the resin composition of the present invention can be processed into a molding material, a sheet or a film, and satisfies properties such as low dielectric constant, low water absorption, and high heat resistance in the fields of electric industry, space / aircraft industry, automobiles and the like. It can be used as a low-dielectric material, an insulating material, a heat-resistant material, a structural material, and the like. In particular, it can be used as a single-sided, double-sided, multi-layer printed circuit board, flexible printed circuit board, build-up board, or the like.
• semiconductor-related materials or optical materials as well as paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal collectors, ion exchange resins, antistatic agents, antioxidants, antifogging agents, and rust preventives.
• Anti-staining agents, bactericides, insect repellents, medical materials, coagulants, surfactants, lubricants, binders for solid fuels, conductive treatment agents, resin modifiers, asphalt modifier plasticizers, sintered binders, etc. Can be applied.
• the curable resin composition of the present invention provides a cured product having high dielectric properties (low dielectric constant, low dielectric loss tangent), high flame retardancy, and satisfies the requirements of halogen-free. .. Therefore, in fields such as the electrical / electronic industry and the space / aircraft industry, it is possible to provide halogen-free materials for high-frequency applications, which have been strongly demanded in recent years, as dielectric materials, insulating materials, heat-resistant materials, structural materials, and the like.
• Synthesis example 1 2.25 mol (292.9 g) of divinylbenzene, 1.32 mol (172.0 g) of ethylvinylbenzene, 11.43 mol (1190.3 g) of styrene, 15.0 mol (1532.0 g) of n-propyl acetate. It was placed in a 5.0 L reactor, 600 mmol of boron trifluoride diethyl ether complex was added at 70 ° C., and the mixture was reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed with pure water three times and devolatile at 60 ° C. to recover the copolymer. The obtained copolymer was weighed, and it was confirmed that 860.8 g of the copolymer A-1 was obtained.
• the obtained copolymer A-1 had Mn of 2060, Mw of 30700, and Mw / Mn of 14.9.
• Mn 2060
• Mw 30700
• Mw / Mn 14.9.
• 13 C-NMR and 1 H-NMR analysis resonance lines derived from each monomer unit were observed in the copolymer A-1.
• the constituent unit of the copolymer A-1 was calculated as follows.
• Synthesis example 2 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, 15.0 mol (1532.0 g) of n-propyl acetate. It was placed in a 5.0 L reactor, 600 mmol of boron trifluoride diethyl ether complex was added at 70 ° C., and the mixture was reacted for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogen carbonate solution, the oil layer was washed with pure water three times and devolatile at 60 ° C. to recover the copolymer. The obtained copolymer was weighed, and it was confirmed that 896.7 g of the copolymer A-2 was obtained.
• the obtained copolymer A-2 had Mn of 2980, Mw of 41300, and Mw / Mn of 13.9.
• the structural unit of the copolymer A-2 was calculated as follows. Structural unit (a1): 30.4 mol% (33.1 wt%) Structural unit (a2): 12.2 mol% (14.2 wt%) Structural unit (a2): 57.4 mol% (52.7 wt%) Structural unit (a1-1): 23.9 mol% (25.9 wt%)
• the obtained copolymer A-3 had Mn of 2500, Mw of 24200, and Mw / Mn of 9.69. Resonance lines derived from the terminal of norbornene were observed in the copolymer A-4. The amount of norbornene-derived terminal group (c1) introduced into the terminal of the soluble polyfunctional vinyl aromatic copolymer was 2.6 (pieces / molecule). Further, the structural unit (a1) derived from divinylbenzene was added to 49.8 mol% (54.1 wt%), the structural unit derived from ethylvinylbenzene (a2) was added to 20.3 mol% (22.4 wt%), and norbornene.
• the obtained copolymer A-4 had Mn of 842, Mw of 3640, and Mw / Mn of 4.32.
• 13C-NMR and 1H-NMR analysis resonance lines of terminal groups derived from t-butyl methacrylate were observed in the copolymer A-4.
• the structural unit (a1) derived from divinylbenzene contained 60.1 mol% of the structural unit (a1) derived from divinylbenzene and 39.9 mol% of the structural unit (a2) derived from ethylvinylbenzene in total (excluding the terminal structural unit).
• the structural unit (a1-1) derived from divinylbenzene having a residual vinyl group contained in the copolymer A-4 was 36.2 mol% (excluding the terminal structural unit).
• Synthesis example 5 Synthesis of Compound B-1 2 mol (432 g) of DOPO and 1 mol (175 g) of 1,4-xylene chloride chloride were added to 2400 g of dichlorobenzene and heated to 150 ° C. to dissolve, and the mixture was heated and stirred for 24 hours. Then, the solution was cooled to room temperature, washed with hexane, the precipitated white solid was filtered off, and dried at 120 ° C. for 6 hours to obtain 492 g of a phosphorus-containing compound (B-1). The phosphorus content was 1.3 wt%.
• Synthesis example 6 Synthesis of Compound B-2 3.5 mol (726 g) of DOPO and 1 mol (266 g) of 1,3,5-trimethyl-2,4,6-tris (chloromethyl) benzene were added to 2400 g of toluene and heated to 150 ° C. It was dissolved and heated and stirred for 24 hours. Then, the solution was cooled to room temperature, washed with hexane, and the precipitated white solid was filtered off and dried at 120 ° C. for 6 hours to obtain 730 g of a phosphorus-containing compound (B-2). The phosphorus content was 11.7 wt%.
• Synthesis example 7 Synthesis of Compound B-3 0.9 mol (195 g) of DOPO was added to 867 ml of toluene, and the mixture was dissolved by heating and stirring at 80 ° C. to prepare a solution in which 0.1 mol (29.8 g) of triphosgene was dissolved in 86.7 g of toluene. Add slowly with a dropping funnel. Then, after stirring for 6 hours while heating and refluxing at 120 ° C., the solution was cooled to room temperature, and the precipitated white solid was filtered off to obtain 624 g of a phosphorus-containing compound (B-3). The phosphorus content was 13.6 wt%.
• Synthesis example 8 Synthesis of Compound B-4 1 mol (202 g) of diphenylphosphine oxide (hereinafter abbreviated as DPPO) is added to 867 ml of toluene, heated and stirred at 80 ° C. to dissolve it, and 0.1 mol (29.8 g) of triphosgen is dissolved in 86.7 g of toluene. The solution dissolved in was slowly added with a dropping funnel. Then, after stirring for 6 hours while heating and refluxing at 120 ° C., the solution was cooled to room temperature, and the precipitated white solid was filtered off to obtain 578 g of a phosphorus-containing compound (B-4). The phosphorus content was 14.2 wt%.
• DPPO diphenylphosphine oxide
• Synthesis example 9 Synthesis of Compound B-5 0.9 mol (261.3 g) of bis (2,6-dimethylphenyl) phosphate was added to 867 ml of toluene, and the mixture was dissolved by heating and stirring at 80 ° C. to dissolve triphosgene (0.1 mol (29.8 g)). Was slowly added in a dropping funnel with a solution of 86.7 g of toluene. Then, after stirring for 6 hours while heating and refluxing at 120 ° C., the solution was cooled to room temperature, and the precipitated white solid was filtered off to obtain 724 g of a phosphorus-containing compound (B-5). The phosphorus content was 11.5 wt%.
• Synthesis example 10 Synthesis of Compound B-6 1 mol (202 g) of DPPO and 0.5 mol (87.5 g) of 1,4-xylene chloride chloride were added to 1200 g of dichlorobenzene and heated to 160 ° C. to dissolve, and the mixture was heated and stirred for 24 hours. .. Then, the solution was cooled to room temperature, and the precipitated white solid was filtered to obtain 60.7 g of a phosphorus-containing compound (B-6). The phosphorus content was 2.1 wt%.
• Synthesis example 11 Synthesis of Compound B-7 867 g of toluene was added to 0.5 mol of HCA-HQ (162 g, manufactured by Sanko Co., Ltd.) and 1.1 mol of sodium hydroxide (44 g), and the mixture was heated and stirred at 50 ° C. for 30 minutes. Then, 1.15 mol of 4-chloromethylstyrene (176 g, AGC Seimi Chemical Co., Ltd.) and 0.075 mol of tetrabutylammonium bromide (24.2 g) were further added, and the mixture was heated and stirred at 50 ° C. for 6 hours.
• HCA-HQ 162 g, manufactured by Sanko Co., Ltd.
• sodium hydroxide 44 g
• Synthesis example 12 Synthesis of Compound B-8 Add 20 g of toluene to 60 g of allylphosphazene compound (SPV-100, manufactured by Otsuka Chemical Co., Ltd.) and 40 g of dicyclopentadiene (manufactured by Sigma-Aldrich), and after stirring, Grubbs catalyst M2a (C848) ( 0.01 g of Grubbs catalyst manufactured by Sigma-Aldrich was added. Then, the solution was heated and stirred at 80 ° C. for 12 hours, the solution was cooled to room temperature, and toluene was distilled off to obtain 102 g of a phosphorus-containing compound (B-8) as a brown viscous liquid. The phosphorus content was 7.2 wt%.
• Synthesis example 13 Synthesis of Compound B-9 20 g of toluene was added to 60 g of compound (B-7) and 40 g of 5-vinyl-2-norbornene (manufactured by Sigma-Aldrich) obtained in Synthesis Example 11, and Grubbs catalyst M2a (C848) was added after stirring. 0.01 g was added. Then, the solution was heated and stirred at 80 ° C. for 12 hours, the solution was cooled to room temperature, and toluene was distilled off to obtain 99 g of a phosphorus-containing compound (B-9) as a brown viscous liquid. The phosphorus content was 2.5 wt%.
• Synthesis example 14 Synthesis of Compound B-10 To 60 g of the compound (B-7) obtained in Synthesis Example 11 and 40 g of dicyclopentadiene (manufactured by Sigma-Aldrich), 20 g of toluene was added, and after stirring, 0.01 g of Grubbs catalyst M2a (C848) was added. rice field. Then, the solution was heated and stirred at 80 ° C. for 12 hours, the solution was cooled to room temperature, and toluene was distilled off to obtain 100 g of a phosphorus-containing compound (B-10) as a brown viscous liquid. The phosphorus content was 2.5 wt%.
• Synthesis example 15 Synthesis of Compound B-11 20 g of toluene was added to 60 g of an allylphosphazene compound (SPV-100, manufactured by Otsuka Chemical Co., Ltd.) and 40 g of 5-vinyl-2-norbornene, and after stirring, Grubbs catalyst M2a (C848) was added to 0. 01 g was added. Then, the solution was heated and stirred at 80 ° C. for 12 hours, the solution was cooled to room temperature, and toluene was distilled off to obtain 100 g of a phosphorus-containing compound (B-11) as a dark brown viscous liquid. The phosphorus content was 7.2 wt%.
• Synthesis example 16 Synthesis of Compound B-12 434 g of toluene was added to 0.4 mol of DOPO (78.6 g) and 0.2 mol of 1,4-phthalaldehyde (26.8 g), and the mixture was stirred with heating under reflux for 5 hours. The above reaction solution was cooled to room temperature, the precipitated solid was filtered off, and dried to obtain 519 g of a white solid. To 283 g of this white solid, 1.5 mol of sodium hydroxide (60 g) and 867 g of toluene were added, and the mixture was heated and stirred at 70 ° C. for 30 minutes.
• the flame retardancy was evaluated by measuring according to the UL-94 flame retardancy test. Those showing flame retardancy of V-1 or higher were marked with " ⁇ ", and those showing flame retardancy of V-1 or higher were marked with "x".
• Example 1 100 parts by weight of the copolymer (A-1) obtained in Synthesis Example 1, 50 parts by weight of the phosphorus-containing compound (B-1) obtained in Synthesis Example 5, and the polymerization initiator perbutyl P (C-1) 1
• a varnish of a curable resin composition was obtained by dissolving 40 parts by weight of the spherical silica (D) as a filler and 0.2 part by weight of an antioxidant in 100 g of toluene.
• the prepared varnish 1 is dropped onto a lower mold, the solvent is devolatile at 135 ° C., the mold is assembled, and a vacuum pressure press is performed at 200 ° C. and 3 MPa for 2 hours to heat cure. I let you.
• Example 2 to 13 Comparative Examples 1, 2, 3
• a varnish of a curable resin composition was obtained in the same manner as in Example 1 except that the compounding formulations shown in Table 1 were used. Then, the test and evaluation were carried out in the same manner as in Example 1. The results obtained by these tests are shown in Table 1.
• the varnish concentration (solid content concentration) was set to 50 wt%.
• (A-1) to (A-4) are copolymers (A) obtained in Synthesis Examples 1 to 4, and (B-1) to (B-12) are obtained in Synthesis Examples 5 to 16. It is a phosphorus-containing compound (B).
• Phosphorus flame retardant (B-13) Aromatic condensed phosphoric acid ester manufactured by Daihachi Chemical Industry Co., Ltd. (trade name: CR-733S, phosphorus concentration 10.9%)
• Phosphorus flame retardant (B-14) Phosphoric acid ester manufactured by Daihachi Chemical Industry Co., Ltd.
• C-1 1,3-bis (butylperoxyisopropyl) benzene (manufactured by NOF CORPORATION
• Terminally modified PPE (E-2): SA9000 manufactured by SABIC Innovative Plastics Co., Ltd. (modified polyphenylene ether in which both terminal hydroxyl groups of polyphenylene ether are modified with methacrylic groups, Mn: 1700, 2 terminal functional groups)
• Antioxidant Tetrakis [methylene-3- (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate] Methane (ADEKA, ADEKA STAB AO-60)
• the curable resin composition of the present invention can provide a halogen-free cured resin or molded product having excellent dielectric properties and flame retardancy. Further, from this curable resin composition, it can be used for a film, a cured product obtained by curing the film, a prepreg, a metal-clad laminate, a printed wiring board, and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Laminated Bodies (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=77390806

Family Applications (1)

Country Status (3)

Cited By (4)

Families Citing this family (1)

Citations (8)

• 2021
  • 2021-02-03 JP JP2022501772A patent/JPWO2021166649A1/ja active Pending
  • 2021-02-03 WO PCT/JP2021/003931 patent/WO2021166649A1/ja not_active Ceased
  • 2021-02-04 TW TW110104166A patent/TW202136406A/zh unknown

Patent Citations (8)

Also Published As

Similar Documents

Legal Events