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WO2025142537A1 - Copolymère aromatique vinylique polyfonctionnel soluble, son procédé de production, et composition de résine durcissable et produit durci de celui-ci - Google Patents

Copolymère aromatique vinylique polyfonctionnel soluble, son procédé de production, et composition de résine durcissable et produit durci de celui-ci Download PDF

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Publication number
WO2025142537A1
WO2025142537A1 PCT/JP2024/044141 JP2024044141W WO2025142537A1 WO 2025142537 A1 WO2025142537 A1 WO 2025142537A1 JP 2024044141 W JP2024044141 W JP 2024044141W WO 2025142537 A1 WO2025142537 A1 WO 2025142537A1
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copolymer
aromatic
styrene
polyfunctional vinyl
compound
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Japanese (ja)
Inventor
悠斗 園山
康幸 ▲高▼尾
新一 岩下
毅志 武田
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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    • 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
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/36—Divinylbenzene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen

Definitions

  • the Lewis acid catalyst (f) is preferably a metal fluoride or a complex thereof
  • the hydroxyl group-containing cocatalyst (g) is preferably a compound of formula (2)
  • the aromatic solvent (h) is preferably a compound of formula (3).
  • R6 and R7 each independently represent an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • R8 represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • R9 and R10 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the present invention will be described in detail below.
  • the soluble polyfunctional aromatic copolymer of the present invention may be simply referred to as the "copolymer.”
  • the structural units derived from the divinyl aromatic compound (a) account for 2 mol % or more and less than 95 mol % of the total of the structural units derived from (a), (b) and (c).
  • the structural unit derived from the divinyl aromatic compound (a) can be a plurality of structures such as one in which two vinyl groups have reacted with only one or two in which two vinyl groups have reacted with each other.
  • the repeating unit represented by the following formula (t1) contains 2 to 80 mol% of a repeating unit in which only one vinyl group has reacted. More preferably, it is 5 to 70 mol%, further preferably, it is 10 to 60 mol%, and particularly preferably, it is 15 to 50 mol%.
  • Aromatic hydrocarbon groups having 6 to 30 carbon atoms are not particularly limited, but include those in which two hydrogen atoms have been removed from single-ring aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and those in which two hydrogen atoms have been removed from condensed ring aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine.
  • single-ring aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyr
  • aromatic compounds may be used, and examples thereof include those in which two hydrogen atoms have been removed from ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.
  • Benzene, naphthalene, biphenyl, and anthracene are preferred. Benzene is even more preferred.
  • the structural units derived from styrene (b) and a monovinyl compound other than styrene (c) are 2 mol% or more and less than 80 mol% of the total of the structural units derived from (a), (b) and (c). It is preferably 5 mol% or more and less than 70 mol%, and more preferably 10 mol% or more and less than 60 mol%. If the molar fraction of the structural units derived from (b) and (c) is less than 2 mol%, the moldability is insufficient, and if it exceeds 80 mol%, the heat resistance of the cured product is insufficient.
  • the vinyl group constituting the above formula (t1) derived from the divinyl aromatic compound (a) acts as a cross-linking component and contributes to the development of heat resistance of the soluble polyfunctional vinyl aromatic copolymer.
  • the structural units derived from styrene (b) and monovinyl compounds other than styrene (c) do not have vinyl groups, since it is believed that polymerization usually proceeds by a 1,2 addition reaction of vinyl groups.
  • the structural units derived from styrene (b) and monovinyl compounds other than styrene (c) do not act as cross-linking components, but contribute to the development of moldability.
  • Divinyl aromatic compound (a), styrene (b) and monovinyl compound other than styrene (c) not only form repeating units containing (t1) by polymerization, but also form end groups, specifically, end groups represented by the following formulae (t2) and (t3) are formed at the end of the polyfunctional vinyl aromatic copolymer.
  • end groups represented by the following formulae (t2) and (t3) are formed at the end of the polyfunctional vinyl aromatic copolymer.
  • the introduction of these end groups can control the properties of the soluble polyfunctional vinyl aromatic copolymer. Therefore, in the polymerization reaction, it is important to control the formation of formulae (t2) and (t3) as end groups, that is, the termination reaction mechanism.
  • R2 and R3 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • Z2 and Z3 each independently represent a vinyl group, a hydrogen atom, or a hydrocarbon group having 1 to 18 carbon atoms. * represents a bond to the main chain, and the same applies hereinafter.
  • R4 and R5 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • Z4 and Z5 each independently represent a vinyl group, a hydrogen atom, or a hydrocarbon group having 1 to 18 carbon atoms.
  • the terminal group of formula (t2) is formed in the process of producing a polyfunctional vinyl aromatic copolymer by electrophilic substitution reaction of a carbocation at the growing end with an aromatic ring of a monomer immediately preceding the growing polymer chain.
  • the terminal group of formula (t2) is formed by an intramolecular electrophilic substitution reaction, and has different terminal structures as follows depending on the structural units derived from the monomers (a), (b), and (c).
  • the terminal structure is represented by the following formula (t2-1).
  • the terminal structure When it consists of a structural unit derived from a divinyl aromatic compound (a) and a structural unit derived from styrene (b) or a monovinyl compound other than styrene (c), the terminal structure is represented by (t2-2) or (t2-3). When both molecules are structural units derived from styrene (b) or a monovinyl compound other than styrene (c), the terminal structure is represented by the following formula (t2-4).
  • R2 and R3 are defined as in formula (t2), and Y1 and Y2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
  • the terminal group of the above formula (t3) is formed by electrophilic substitution reaction of the growing end carbocation with an aromatic compound during the production process of the polyfunctional vinyl aromatic copolymer. Not only the aromatic monomers (a), (b), and (c), but also the aromatic solvent (h) can participate in this reaction.
  • the terminal group of formula (t3) is formed by an electrophilic substitution reaction involving two molecules, and has different terminal structures as follows depending on the structural units derived from the monomers (a), (b), and (c) and the aromatic solvent (h).
  • the terminal structure is represented by (t3-2).
  • the terminal structure represented by (t3-3) is obtained.
  • the terminal structure is represented by the following formula (t3-4). That is, the terminal group of formula (t3) represents the sum of the terminal groups of (t3-1) to (t3-4).
  • R4 and R5 are defined as in formula (t3), and Y3 and Y4 represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
  • Aromatic hydrocarbon groups having 6 to 30 carbon atoms are not particularly limited, but include those in which two hydrogen atoms have been removed from single-ring aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and those in which two hydrogen atoms have been removed from condensed ring aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine.
  • single-ring aromatic compounds such as benzene, furan, pyrrole, thiophene, imidazole, pyr
  • the terminal groups of the soluble polyfunctional vinyl copolymer satisfy the relationship of the following formula 1.
  • the structures t2 and t3 account for more than 5 mol% of the terminal structure.
  • the repeating structural unit t1 and the terminal structures t2 and t3 satisfy the relationship of formula 1, low dielectric properties are exhibited and resistance to thermal oxidative degradation is significantly improved.
  • the cause is unknown, it is speculated that the heat degradation resistance is improved by introducing a low-polarity, rigid aromatic ring into the terminal structure.
  • the ratio is preferably 0.10 or more, more preferably 0.15 or more, while the upper limit is preferably less than 0.50, more preferably less than 0.45.
  • the mole percentages of (t1), (t2) and (t3) relative to the total of the divinyl aromatic compound (a), styrene (b) and monovinyl compound other than styrene (c) are in the range of 2 to 80 mole percent. This means the content of vinyl groups and terminal groups in the soluble polyfunctional vinyl aromatic copolymer. If this mole percentage is less than 2 mole percent, the heat resistance decreases, and if it is more than 80 mole percent, the interlayer peel strength decreases when the copolymer is laminated. It is preferably 5 to 80 mole percent, more preferably 10 to 70 mole percent, and particularly preferably 15 to 65 mole percent. The preferred mole percentages are the same even when the copolymer contains structural units derived from monomers other than (a), (b) and (c).
  • the amount of vinyl-containing end groups (tv) introduced is 0.2 or more per molecule.
  • the vinyl-containing end groups (tv) are (t2) in which Z2 and/or Z3 are vinyl groups, and (t3) in which Z4 and/or Z5 are vinyl groups.
  • the amount of vinyl-containing end groups (tv) introduced means the total of formulas (t2-1), (t2-2), (t2-3), (t3-1), (t3-2), and (t3-3). If the amount of vinyl-containing end groups (tv) introduced is less than 0.2, the curability and heat resistance are reduced. It is preferably 0.5 or more, more preferably 0.6 or more per molecule.
  • the number average molecular weight (Mn: number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) of the soluble polyfunctional vinyl aromatic copolymer is preferably 500 to 10,000, more preferably 600 to 9,000, and even more preferably 700 to 8,000. If Mn is less than 500, the amount of monofunctional copolymer components contained in the soluble polyfunctional vinyl aromatic copolymer increases, and the heat resistance of the cured product tends to decrease. If Mn is more than 10,000, gel is more likely to be formed and the viscosity increases, so that moldability tends to decrease.
  • Mw/Mn The value of the molecular weight distribution (Mw/Mn), which is expressed as the ratio of the weight average molecular weight (Mw: weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) to Mn, is 40.0 or less, preferably 35.0 or less, more preferably 1.5 to 30.0, and most preferably 2.0 to 25.0. If Mw/Mn is more than 40.0, the processing characteristics of the soluble polyfunctional vinyl aromatic copolymer tend to deteriorate and gel tends to occur.
  • the copolymer is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform as a solvent, but is preferably soluble in all of the above solvents.
  • soluble in a solvent means that 5 g or more of the 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.
  • the method for producing a soluble polyfunctional vinyl aromatic copolymer of the present invention is a method for producing a polyfunctional vinyl aromatic copolymer by polymerizing a divinyl aromatic compound (a), styrene (b) and a monovinyl compound other than styrene (c) in the presence of a Lewis acid catalyst (f), a cocatalyst (g) containing a hydroxyl group, and an aromatic solvent (h), and is characterized in that the polymerization is carried out at a temperature of -20 to 120°C.
  • the Lewis acid catalyst (f) acts as a catalyst
  • the cocatalyst (g) containing a hydroxyl group acts as a cocatalyst.
  • the monovinyl compounds are styrene (b) and monovinyl compounds other than styrene (c).
  • Styrene (b) is essential as a monovinyl compound, and it is also necessary to use a monovinyl compound other than styrene (c) in combination.
  • Styrene (b) acts as a monomer component to impart low dielectric properties and thermal oxidative degradation resistance to the soluble polyfunctional vinyl aromatic copolymer, and acts as a chain transfer agent to control the molecular weight of the soluble polyfunctional vinyl aromatic copolymer and introduce vinyl groups to the terminals of the soluble polyfunctional vinyl aromatic copolymer.
  • Monovinyl compounds other than styrene (c) improve the solvent solubility and processability of the soluble polyfunctional vinyl aromatic copolymer.
  • monovinyl compounds (c) other than styrene include, but are not limited to, vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl, as long as they are monomers other than styrene having one vinyl group; nucleus alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene; and monovinyl aliphatic compounds such as propylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, and 2,4,4-trimethylpentene-1.
  • vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl
  • Ethylvinylbenzene (including each positional isomer or a mixture thereof), ethylvinylbiphenyl (including each positional isomer or a mixture thereof), and ethylvinylnaphthalene (including each positional isomer or a mixture thereof) are preferred because they prevent gelation of the soluble polyfunctional vinyl aromatic copolymer, have a high effect of improving solvent solubility and processability, are low in cost, and are easily available. More preferably, from the viewpoint of dielectric properties and cost, it is ethylvinylbenzene (m-isomer, p-isomer, or a mixture of these positional isomers).
  • a trivinyl aromatic compound, a trivinyl aliphatic compound and a divinyl aliphatic compound can be used to introduce structural units derived from other monomer components (d) into the soluble polyfunctional vinyl aromatic copolymer, so long as the effect of the present invention is not impaired.
  • Other monomer components (d) include, for example, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triallyl isocyanurate, etc. These can be used alone or in combination of two or more.
  • the molar fraction of the other monomer component (d) relative to the sum of all monomer components (a), (b), (c) and (d) is preferably less than 30 mol%.
  • the molar fraction of the repeating units derived from the other monomer component (d) relative to the sum of structural units derived from all monomer components (a), (b), (c) and (d) constituting the copolymer is preferably less than 30 mol%.
  • the ratio of the essential monomer components (a), (b), and (c) used is such that the divinyl aromatic compound (a) is used in an amount of 2 mol% or more and less than 95 mol% relative to the total of (a), (b), and (c), and the combined amount of styrene (b) and monovinyl compound other than styrene (c) is used in an amount of 5 mol% or more and less than 98 mol%, and these monomer components (a), (b), and (c) are polymerized at a temperature of -20 to 120°C.
  • one or more hydroxyl group-containing cocatalysts (g) represented by the following formula 2 are used as the cocatalyst.
  • R6 and R7 each independently represent an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • R8 represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. In the case of an alkyl group, it is preferably an alkyl group having 1 to 6 carbon atoms.
  • cocatalyst (g) containing a hydroxyl group examples include aromatic compounds containing a hydroxyl group, such as 1-phenylethanol and 2-phenyl-2-propanol, and chain hydrocarbon compounds containing a hydroxyl group, such as 2-propanol and tert-butyl alcohol.
  • aromatic compounds containing a hydroxyl group such as 1-phenylethanol and 2-phenyl-2-propanol
  • chain hydrocarbon compounds containing a hydroxyl group such as 2-propanol and tert-butyl alcohol.
  • one or more compounds selected from the group consisting of aromatic compounds are preferably used, since they act synergistically with the Lewis acid catalyst (f) and can easily control the polymerization rate and the molecular weight distribution of the polymer.
  • these cocatalysts (g) containing a hydroxyl group can be used.
  • radical polymerization initiator (i) may be used alone or in combination of two or more kinds.
  • the curable reactive resin (j) is preferably a polyvinylbenzyl resin, a curable vinyl resin, a curable polyphenylene ether resin, an epoxy resin, or one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule
  • the thermoplastic resin is preferably polystyrene, a polyphenylene ether resin, a styrene-ethylene-propylene copolymer, a styrene-ethylene-butylene copolymer, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-butadiene copolymer, or a hydrogenated styrene-isoprene copolymer.
  • the substituent having a carbon-carbon unsaturated double bond is a substituent selected from the group consisting of a vinylbenzyl group, a vinyl group, an acrylate group, and a methacrylate group.
  • the average number of unsaturated hydrocarbon groups (number of terminal functional groups) possessed by one molecule of the modified polyphenylene ether compound containing an unsaturated hydrocarbon group at the end is not particularly limited. From the viewpoint of the balance between the heat resistance of the cured product and the storage stability and fluidity of the curable resin composition, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3.
  • the toughness and moldability of the cured product of the obtained curable resin composition are higher. This is because the number average molecular weight of the curable polyphenylene ether resin is within this range, and since it is a relatively low molecular weight, the flowability is improved while maintaining toughness. When a normal polyphenylene ether having such a low molecular weight is used, the heat resistance and toughness of the cured product tend to decrease.
  • the above curable polyphenylene ether resin has a polymerizable unsaturated double bond at the end, by copolymerizing or curing it with a vinyl-based curable resin such as the copolymer of the present invention, the crosslinking of both proceeds favorably, and a cured product with sufficiently high heat resistance and toughness is obtained. Therefore, the cured product of the obtained curable resin composition has excellent heat resistance and toughness.
  • the curable reactive resin (j) is an epoxy resin
  • it is preferably one or more epoxy resins (jb) selected from the group consisting of epoxy resins having two or more epoxy groups in one molecule.
  • (jb) 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 does not contain a halogenated epoxy resin, but it may be blended as necessary as long as it does not impair the effects of the present invention.
  • the curable reactive resin (j) is one or more vinyl compounds (jd) having one or more polymerizable unsaturated hydrocarbon groups in the molecule
  • (jd) may be any compound that can form crosslinks and be cured by reacting with the polyfunctional vinyl aromatic copolymer of the present invention.
  • the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferable is a compound having two or more carbon-carbon unsaturated double bonds in the molecule.
  • the vinyl compounds (jd) as the curable reactive resin preferably have a weight average molecular weight (Mw) of 100 to 5,000, more preferably 100 to 4,000, and even more preferably 100 to 3,000. If the Mw is less than 100, (jd) may be easily volatilized from the compounding components of the curable resin composition. If the Mw exceeds 5,000, the viscosity of the varnish of the curable resin composition and the melt viscosity during heat molding may be too high. Therefore, if the Mw of (jd) is within this range, a curable resin composition with excellent heat resistance of the cured product can be obtained. This is thought to be because crosslinks can be suitably formed by the reaction of the soluble polyfunctional vinyl aromatic copolymer with (jd). Note that the Mw may be measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC) may be mentioned.
  • GPC gel permeation chromatography
  • the average number of carbon-carbon unsaturated double bonds (number of terminal double bonds) per molecule of vinyl compounds (jd) as curable reactive resins varies depending on the Mw of (jd), but 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. If the number of terminal double bonds is too large, the reactivity becomes too high, and problems such as reduced storage stability of the curable resin composition or reduced flowability of the curable resin composition may occur.
  • Vinyl compounds (jd) as curable reactive resins include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds), and vinylbenzyl compounds such as styrene and divinylbenzene having vinylbenzyl groups in the molecule. Among these, compounds having two or more carbon-carbon double bonds in the molecule are preferred.
  • TAIC triallyl isocyanurate
  • TAIC triallyl isocyanurate
  • polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule polyfunctional acrylate compounds having two or more acrylic groups in the molecule
  • vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds)
  • vinylbenzyl compounds such
  • the content of the soluble polyfunctional vinyl aromatic copolymer is preferably 30 to 90 parts by mass, more preferably 50 to 90 parts by mass, per 100 parts by mass of the total of the soluble polyfunctional vinyl aromatic copolymer and the vinyl compounds (jd) as the curable reactive resin.
  • the content of the vinyl compounds (jd) as the curable reactive resin is preferably 10 to 70 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the total of the soluble polyfunctional vinyl aromatic copolymer and (jd).
  • the content ratio of the soluble polyfunctional vinyl aromatic copolymer to the vinyl compounds (jd) as the curable reactive resin is preferably 90:10 to 30:70, more preferably 90:10 to 50:50, by mass.
  • the curable resin composition will have better heat resistance and flame retardancy of the cured product. This is believed to be due to the favorable progress of the curing reaction between the soluble polyfunctional vinyl aromatic copolymer and the vinyl compounds (jd) as the curable reactive resin.
  • the curable resin composition of the present invention can be blended with a known flame retardant (l).
  • the flame retardant (l) can further increase the flame retardancy of the cured product of the curable resin composition.
  • the flame retardant (l) is not particularly limited. Specifically, in fields where halogen-based flame retardants such as bromine-based flame retardants are used, for example, ethylene dipentabromobenzene, ethylene bis tetrabromoimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene, which have a melting point of 300°C or more, are preferred. It is believed that the use of a halogen-based flame retardant can suppress the detachment of halogen at high temperatures and suppress the decrease in heat resistance.
  • phosphate ester-based flame retardants In fields where halogen-free is required, phosphate ester-based flame retardants, phosphazene-based flame retardants, and phosphinate-based flame retardants can be mentioned.
  • a specific example of a phosphate ester-based flame retardant is condensed phosphate ester of dixylenyl phosphate.
  • a specific example of a phosphazene-based flame retardant is phenoxyphosphazene.
  • phosphinate-based flame retardants include, for example, metal phosphinates of aluminum dialkylphosphinate. Each of the exemplified flame retardants may be used alone or in combination of two or more.
  • the curable resin composition of the present invention can be blended with a known filler (m).
  • the filler (m) include those added to enhance the heat resistance and flame retardancy of the cured product of the curable resin composition, and are not particularly limited. By including the filler (m), the heat resistance and flame retardancy can be further enhanced.
  • Specific examples 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, and calcium carbonate. Among these, silica, mica, and talc are preferred, and spherical silica is more preferred.
  • the content of the filler (m) is preferably 10 to 200 parts by mass, and more preferably 30 to 150 parts by mass, per 100 parts by mass of the total of the organic components such as monomers and the flame retardant (l).
  • a coupling agent can be used in the curable composite material to improve adhesion at the interface between the resin and the substrate.
  • Common coupling agents can be used, such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents.
  • a method for producing a curable composite material may include, for example, a method in which the curable resin composition of the present invention and, if necessary, other components are uniformly dissolved or dispersed in the above-mentioned aromatic or ketone solvent or a mixture thereof, impregnated into a substrate, and then dried. Impregnation is performed by immersion (dipping), coating, etc. Impregnation can be repeated multiple times as necessary, and in this case, impregnation can be repeated using multiple solutions with different compositions and concentrations, allowing adjustment to the final desired resin composition and resin amount.
  • a cured composite material is obtained by curing the curable composite material by heating or other methods.
  • a cured composite material of the desired thickness can be obtained by stacking multiple sheets of curable composite material, bonding each layer together under heat and pressure, and simultaneously thermally curing the layers.
  • Lamination molding and curing are usually performed simultaneously using a heat press or the like, but both can also be performed separately. In other words, an uncured or semi-cured composite material obtained in advance by lamination molding can be cured by heat treatment or another method.
  • the curing, or molding and curing, of the curable resin composition or curable composite material of the present invention can be carried out preferably at a temperature of 80 to 300°C, at a pressure of 0.1 to 1000 kg/cm2, and for a time of 1 minute to 10 hours, and more preferably at a temperature of 150 to 250°C, at a pressure of 1 to 500 kg/cm2, and for a time of 1 minute to 5 hours.
  • the resin composition containing the soluble vinyl copolymer of the present invention can also be used in a laminate. Specifically, it is composed of a layer of the above-mentioned cured composite material 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, and more preferably 3 to 105 ⁇ m.
  • a method for producing a laminate for example, a method can be mentioned in which a curable composite material obtained from the curable resin composition of the present invention and a substrate, and a metal foil are laminated in a layer configuration according to the purpose, and each layer is bonded under heat and pressure while being thermally cured.
  • the cured composite material and the metal foil are laminated in an arbitrary layer configuration.
  • the metal foil can be used as both a surface layer and an intermediate layer. It is also possible to make a multi-layer structure by repeating the lamination and curing multiple times.
  • the curable resin composition of the present invention can be formed into a film by molding it into a film.
  • the thickness is not particularly limited, but is preferably in the range of 3 to 200 ⁇ m, and more preferably 5 to 105 ⁇ m.
  • the method for producing the film is not particularly limited, and examples include a method in which the curable resin composition is uniformly dissolved or dispersed in an aromatic or ketone solvent or a mixture thereof, and then coated onto a resin film such as a PET film, followed by drying.
  • the coating can be repeated multiple times as necessary, and in this case, it is possible to repeatedly coat the film using multiple solutions with different compositions and concentrations, and ultimately adjust the resin composition and amount to the desired one.
  • the resin-coated metal foil is composed of the curable resin composition of the present invention and a metal foil.
  • the metal foil used here include copper foil and aluminum foil.
  • the thickness is preferably in the range of 3 to 200 ⁇ m, and more preferably 5 to 105 ⁇ m.
  • the method for producing resin-coated metal foil is not particularly limited, and examples include a method in which a curable resin composition is uniformly dissolved or dispersed in an aromatic or ketone solvent or a mixture thereof, and then coated on metal foil and dried.
  • the coating can be repeated multiple times as necessary. In this case, coating can be repeated using multiple solutions with different compositions and concentrations to finally adjust the resin composition and amount to the desired one.
  • the terminal group was calculated by calculating the amount of a specific structural unit introduced at the terminal from the data on the total amount of each structural unit introduced into the copolymer obtained by GC analysis in addition to the results of 13C-NMR and 1H-NMR measurements, and then calculating the number of terminal groups of the specific structural unit contained in one molecule of the polyfunctional vinyl aromatic copolymer from the amount of the specific structural unit introduced at the terminal and the number average molecular weight obtained by the above GPC measurement.
  • the monomers and solvents used were purchased as reagents.
  • the radical polymerization initiator used in the formulation was VR-110 (Fujifilm Wako Pure Chemicals, azo-based polymerization initiator).
  • Example 1 Synthesis of Copolymer 1 In a 1000 mL reaction vessel, divinylbenzene (18 g; 0.14 mol), Ethylvinylbenzene (15 g; 0.11 mol), Styrene (72 g; 0.69 mol), Toluene (358 g; 3.89 mol), Boron trifluoride diethyl ether complex (6 g), 1-Phenylethanol (2 g; 0.02 mol), Water (0.7 g) was added and the mixture was allowed to react for 4 hours at 40° C. The polymerization solution was terminated with methanol and an aqueous solution of sodium bicarbonate, and the oil layer was washed three times with pure water and devolatilized under reduced pressure at 40° C.
  • Copolymer 1 The amount of consumed monomer of the obtained copolymer was quantified using gas chromatography to obtain the molar ratio of units in the copolymer.
  • the molar fraction of the terminal structure was determined using NMR shown in Figure 1.
  • Mn and Mw were calculated using GPC shown in Figure 2. These results are shown in Table 1.
  • Example 2 Synthesis of Copolymer 2 Divinylbenzene (28 g), ethylvinylbenzene (17 g), styrene (115 g), toluene (119 g), boron trifluoride diethyl ether complex (5 g), 1-phenylethanol (10 g), and water (1.1 g) were placed in a 500 mL reaction vessel and reacted at 40 ° C. for 4 hours. After the polymerization solution was stopped with methanol and an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, and the copolymer was recovered by degassing under reduced pressure at 40 ° C. The obtained copolymer was weighed to obtain Copolymer 2. The obtained Copolymer 2 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

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  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'objectif de la présente invention est de fournir : un nouveau copolymère aromatique vinylique polyfonctionnel soluble qui présente une résistance améliorée à la détérioration par oxydation thermique de caractéristiques diélectriques tout en ayant des caractéristiques diélectriques élevées ; son procédé de production ; et une composition de résine durcissable qui contient le copolymère.　L'invention concerne un copolymère aromatique vinylique polyfonctionnel soluble qui contient des motifs structuraux qui sont dérivés d'un composé aromatique divinylique (a), du styrène (b) et d'un composé monovinylique (c) autre que le styrène. Ce copolymère aromatique vinylique polyfonctionnel soluble est caractérisé en ce qu'il contient des groupes terminaux représentés par les formules (t2) et (t3) aux extrémités du copolymère, et est soluble dans un solvant.
PCT/JP2024/044141 2023-12-27 2024-12-13 Copolymère aromatique vinylique polyfonctionnel soluble, son procédé de production, et composition de résine durcissable et produit durci de celui-ci Pending WO2025142537A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007332273A (ja) * 2006-06-15 2007-12-27 Nippon Steel Chem Co Ltd 可溶性多官能ビニル芳香族共重合体及びその製造方法
WO2018181842A1 (fr) * 2017-03-30 2018-10-04 新日鉄住金化学株式会社 Copolymère aromatique vinylique polyfonctionnel soluble, son procédé de production, composition de résine durcissable et produit durci à base de celui-ci

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007332273A (ja) * 2006-06-15 2007-12-27 Nippon Steel Chem Co Ltd 可溶性多官能ビニル芳香族共重合体及びその製造方法
WO2018181842A1 (fr) * 2017-03-30 2018-10-04 新日鉄住金化学株式会社 Copolymère aromatique vinylique polyfonctionnel soluble, son procédé de production, composition de résine durcissable et produit durci à base de celui-ci

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