WO2023189949A1 - Copolymère aromatique vinylique multifonctionnel - Google Patents

Copolymère aromatique vinylique multifonctionnel Download PDF

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WO2023189949A1
WO2023189949A1 PCT/JP2023/011253 JP2023011253W WO2023189949A1 WO 2023189949 A1 WO2023189949 A1 WO 2023189949A1 JP 2023011253 W JP2023011253 W JP 2023011253W WO 2023189949 A1 WO2023189949 A1 WO 2023189949A1
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vinyl aromatic
curable
mol
molecular weight
polyfunctional vinyl
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PCT/JP2023/011253
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English (en)
Japanese (ja)
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千豊 末満
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旭化成株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present disclosure relates to polyfunctional vinyl aromatic copolymers and the like.
  • Patent Document 1 discloses a soluble polyfunctional vinyl aromatic copolymer obtained by polymerizing a divinyl aromatic compound and a monovinyl aromatic compound in the presence of a Lewis acid catalyst. ing.
  • Patent Document 2 proposes a polyfunctional vinyl aromatic copolymer obtained by polymerizing not only a divinyl aromatic compound and a vinyl aromatic compound but also a cycloolefin compound.
  • the present disclosure provides a polyfunctional vinyl aromatic copolymer that can provide a prepreg with excellent dielectric properties and heat resistance and few voids, and a laminate having good appearance and high interlaminar peel strength. , and a curable resin composition containing the same.
  • the polyfunctional vinyl aromatic copolymer according to item 8 wherein the alkylstyrene is 4-n-octylstyrene.
  • the polyfunctional vinyl aromatic copolymer according to any one of items 1 to 9 A curable resin composition containing one or more selected from the group consisting of a curable reactive compound, a curable reactive resin, a thermoplastic resin, and a radical polymerization initiator.
  • the curable resin composition according to item 10 which contains a curable reactive compound, and the curable reactive compound is trialkenyl isocyanurate and/or trialkenyl cyanurate.
  • the curable resin composition according to item 10 or 11 which contains a curable reactive resin, and the curable reactive resin is polyphenylene ether.
  • a curable composite material comprising the curable resin composition according to any one of items 10 to 13 and a base material, wherein the base material contains 1% by mass based on the total mass of the curable composite material.
  • a curable composite material comprising ⁇ 99% by mass.
  • a laminate comprising a plurality of layers of the cured composite material according to item 16.
  • a metal-clad laminate comprising a layer of the curable composite material according to item 15 and a metal foil layer.
  • a resin-coated metal foil comprising a metal foil and a film obtained by curing the curable resin composition according to any one of items 10 to 13 on one side of the metal foil.
  • a polyfunctional vinyl aromatic copolymer can provide a prepreg that has excellent dielectric properties and heat resistance and has few voids, and a laminate that has good appearance and high interlayer peel strength. , and a curable resin composition containing the same.
  • this embodiment a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described. Since the following embodiment is one aspect of the present invention, the present invention is not limited only to the following embodiment. Therefore, the following embodiments can be modified and implemented as appropriate within the scope of the gist of the present invention. Further, in the present disclosure, “ ⁇ ” means that unless otherwise specified, the numerical values at both ends thereof are included as an upper limit value and a lower limit value. In the present disclosure, the upper and lower limits of the numerical ranges can be arbitrarily combined.
  • the polyfunctional vinyl aromatic copolymer of the present disclosure has a structural unit (a) derived from a divinyl aromatic compound and a structural unit (b) derived from a monovinyl aromatic compound.
  • structural unit (a) derived from the divinyl aromatic compound 60 mol% or more is m-form.
  • m-form refers to a structural unit derived from a divinyl aromatic compound in which two vinyl groups are coordinated to each other at the m-position (meta-position).
  • the polyfunctional vinyl aromatic copolymer has a molecular weight distribution dispersity (Mw/Mn) of 2.5 or less, which is expressed as a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).
  • the molecular weight distribution of conventional polyfunctional vinyl aromatic copolymers is widely multimodal in the high molecular weight region, that is, they contain many high molecular weight components that are crosslinked during polymerization; Since the high-molecular weight components are poorly soluble in the varnish solvent, it is thought that the undissolved high-molecular weight components become a factor in the generation of voids.
  • the m-isomer ratio of the structural unit (a) derived from the divinyl aromatic compound is 60 mol% or more, so that the growing terminals are removed during polymerization.
  • the side reaction of reacting with the vinyl group of the structural unit (a) derived from the divinyl aromatic compound to form a crosslinked structure is suppressed, and a polyfunctional vinyl copolymer with a sharp molecular weight distribution without a crosslinked structure is obtained. Since the obtained polyfunctional vinyl copolymer contains almost no crosslinked structure, the amount of voids generated during prepreg production is reduced, and when a laminate is produced, the appearance and interlayer peel strength are improved.
  • the m-isomer ratio in the structural unit (a) derived from the divinyl aromatic compound is 60 mol% or more, one vinyl group of the divinyl aromatic compound is not used for crosslinking during polymerization and remains until curing. can do.
  • the polyfunctional vinyl aromatic copolymer of the present disclosure can provide prepregs with excellent dielectric properties and heat resistance and few voids, and laminates with good appearance and high interlayer peel strength. it is conceivable that.
  • the structure of the structural unit (a) is not particularly limited as long as it is derived from a divinyl aromatic compound, but preferably includes a structure represented by the following chemical formula (1).
  • R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and n represents an integer of 1 or more.
  • the structure of the structural unit (a) may include, for example, a structure represented by the following chemical formula (1'), in which two vinyl groups derived from a divinyl aromatic compound have both reacted.
  • R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • n represents an integer of 1 or more.
  • R 1 is each independently preferably a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, such as a phenylene group, a naphthylene group, or a divalent biphenyl group. , structural isomers thereof, and combinations thereof, and from the viewpoint of solubility, a phenylene group is preferable.
  • Each n is independently an integer of 1 or more, and the upper limit of n may be, for example, 100 or less, although it is not limited.
  • the structure of the above structural unit (b) may be derived from a monovinyl aromatic compound (excluding those corresponding to "alkylstyrene having an alkyl group having 3 to 20 carbon atoms" in structural unit (c)).
  • a monovinyl aromatic compound excluding those corresponding to "alkylstyrene having an alkyl group having 3 to 20 carbon atoms" in structural unit (c)
  • R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • n represents an integer of 1 or more.
  • R 2 preferably represents a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group, a monovalent biphenyl group, structural isomers thereof, and From the viewpoint of solubility, phenyl group is preferred.
  • n is an integer of 1 or more, and the upper limit of n may be, for example, 100 or less, although it is not limited.
  • the structural units (a) and structural units (b) may be arranged alternately, randomly, in a block or graft form, or in a combination thereof.
  • the polyfunctional vinyl aromatic copolymer of the present disclosure contains a structural unit (c) derived from an alkyl styrene having an alkyl group having 3 to 20 carbon atoms in an amount of 1 mol% to 99 mol% based on a total of 100 mol% of all structural units. It is preferable to include.
  • the alkyl group having 3 to 20 carbon atoms may be a straight-chain or branched alkyl group, preferably a straight-chain alkyl group.
  • the number of carbon atoms is preferably 6 to 10, more preferably 6 to 8, from the viewpoint of achieving both improvement in heat resistance and strength and ease of handling.
  • the alkyl group includes a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and structural isomers thereof.
  • 4-n-octylstyrene having 8 carbon atoms is particularly preferred.
  • the polyfunctional vinyl aromatic copolymer can provide a laminate or the like having higher heat resistance and strength.
  • the content of structural units derived from alkyl styrene is preferably 1 mol% to 99 mol%, more preferably 5 mol% to 99 mol%, even more preferably 10 mol% to 99 mol%, based on the total 100 mol% of all structural units. .
  • the polyfunctional vinyl aromatic copolymer can provide a laminate or the like having higher heat resistance and strength.
  • the vinyl group of the structural unit (a) derived from the divinyl aromatic compound acts as a crosslinking component and contributes to improving the heat resistance of the polyfunctional vinyl aromatic copolymer.
  • the structural unit derived from the monovinyl aromatic compound (b) does not have a vinyl group and therefore does not act as a crosslinking component, improving compatibility with curable resins such as modified PPE and improving solubility in varnish solvents. , contributes to improving the formability of prepregs, laminates, etc.
  • the "m-form” refers to a structural unit derived from a divinyl aromatic compound in which two vinyl groups are at the m-position (meta position) with respect to each other. That is, the general formula (1) refers to a structural isomer in which the bond of the R 1 group to the main chain and the vinyl group are at the m-position (meta position) to each other, and the general formula (1') refers to a structural isomer in which the bond to the main chain of the R 1 group and the vinyl group are at the m-position (meta position).
  • the ratio occupied by the m-form structural isomer (hereinafter referred to as m-form ratio) is 60 mol% or more, that is, 60 mol% or more and 100 mol% or less, preferably 65 mol% or more. It is 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less. This further improves dielectric properties, heat resistance, appearance, and interlayer peel strength.
  • the m-isomer ratio is preferably less than 100 mol%, more preferably 99 mol% or less, and even more preferably 96 mol% or less.
  • the m-isomer ratio is, for example, 60 mol% or more and less than 100 mol%, preferably 65 mol% or more and 99% or less, more preferably 70 mol% or more and 96 mol% or less.
  • the m-form ratio in the structural unit (a) derived from a divinyl aromatic compound is due to the m-form ratio contained in the divinyl aromatic compound used as a monomer during polymerization. That is, in order to synthesize a polyfunctional vinyl copolymer having the structural unit (a) derived from a divinyl aromatic compound having the above m-isomer ratio, the m-isomer ratio is preferably 60 mol% or more and 100 mol% or less, or more.
  • a divinyl aromatic compound monomer is used.
  • the structural unit (a) derived from the divinyl aromatic compound may be a plurality of structural units such as one in which only one vinyl group represented by the general formula (1) is reacted, or one in which two vinyl groups represented by the general formula (1') are reacted. It can be the structure of Among these, the amount of repeating units in which only one vinyl group represented by general formula (1) has reacted is preferably 1 mol% with respect to the total of structural units (a), (b), and (c). ⁇ 95 mol%, more preferably 5 mol% ⁇ 50 mol%, even more preferably 5 mol% ⁇ 40 mol%, even more preferably 5 mol% ⁇ 35 mol%.
  • the side reaction in which the growing end reacts with the vinyl group of the structural unit (a) derived from the divinyl aromatic compound to form a crosslinked structure during polymerization is suppressed, resulting in a sharp molecular weight distribution with less crosslinked structure.
  • a polyfunctional vinyl copolymer can be obtained.
  • the vinyl groups that remain unused for crosslinking during curing can be reduced, the dielectric loss tangent can be further reduced.
  • the amount of structural unit (b) derived from the monovinyl aromatic compound is preferably 5 mol% to 99 mol%, more preferably 50 mol% to 95 mol%, based on the total of structural units (a), (b) and (c). , more preferably 60 mol% to 95 mol%, even more preferably 65 mol% to 95 mol%.
  • the polyfunctional vinyl aromatic copolymer has excellent compatibility with curable resins such as modified PPE, solubility in varnish solvents, and moldability into prepregs and laminates.
  • the structural unit (a) derived from a divinyl aromatic compound and the structural unit (b) derived from a monovinyl aromatic compound may each include one type or a combination of multiple types.
  • the divinyl aromatic compound are not limited as long as it is an aromatic compound having two vinyl groups, but divinylbenzene, divinylnaphthalene, divinylbiphenyl, structural isomers thereof, and mixtures thereof are preferably used, Divinylbenzene is more preferred from the viewpoint of solubility.
  • monovinyl aromatic compounds include, but are not limited to, aromatic compounds having one vinyl group, such as vinyl aromatic compounds such as styrene, vinylnaphthalene, and vinylbiphenyl; o-methylstyrene, m-methylstyrene, Examples include alkyl-substituted vinyl aromatic compounds such as p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene.
  • styrene, ethylvinylbenzene each positional isomer or mixtures thereof.
  • the monovinyl aromatic compound may be styrene-free.
  • the polyfunctional vinyl aromatic copolymer includes, in addition to divinyl aromatic compounds and monovinyl aromatic compounds, trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds. It may have a structural unit derived from other monomer components such as group compounds.
  • the number average molecular weight (Mn: standard polystyrene equivalent number average molecular weight measured using gel permeation chromatography) of the polyfunctional vinyl aromatic copolymer is preferably 300 to 7,000, more preferably 350 to 6, 000, more preferably 400 to 4,000.
  • Mn is 300 or more, the molecular weight is sufficiently high and the strength of the cured product tends to be increased, and when Mn is 7,000 or less, moldability tends to be improved.
  • the value of the dispersity of the molecular weight distribution (Mw/Mn) which is expressed as the ratio of the weight average molecular weight (Mw: standard polystyrene equivalent weight average molecular weight measured using gel permeation chromatography) and Mn, is 3.
  • the curing reactivity of the m-form double bond is mild, so if the m-form ratio is 60% or more, metal-clad laminates and resin
  • the resin When manufacturing a coated metal foil, it is possible to have appropriate reactivity during curing, slowing down the rate of increase in the viscosity of the resin layer, and by having Mw/Mn of 1 or more and 2.5 or less, the resin can be further improved.
  • the rate of increase in viscosity of the layer can be slowed down. Due to the synergistic effect of both, the resin penetrates into the roughened surface of the copper foil while maintaining appropriate fluidity until the middle stage of the curing reaction, and tends to be uniformly cured. Furthermore, since curing is completed after penetration, the anchoring effect is enhanced, resulting in good heat resistance, which is thought to increase interlayer peel strength.
  • the molecular weight distribution exhibits a unimodal differential molecular weight distribution.
  • the polymer having a molecular weight of 10,000 or more accounts for 60% or less of the total.
  • the fact that the molecular weight distribution is monomodal and that the molecular weight of the polymer with a molecular weight of 10,000 or more is within the above range means that it contains almost no high molecular weight components crosslinked during polymerization, which improves the solubility in varnish solvents.
  • the method for producing a soluble polyfunctional vinyl aromatic copolymer of the present disclosure involves polymerizing monomers such as a divinyl aromatic compound and a monovinyl aromatic compound in the presence of a catalyst and a cocatalyst to produce a polyfunctional vinyl aromatic copolymer.
  • monomers such as a divinyl aromatic compound and a monovinyl aromatic compound
  • examples include methods for producing coalescence. More specifically, the divinyl aromatic compound is used at 1 mol% or more and less than 95 mol%, the monovinyl aromatic compound is used at 5 mol% or more and less than 99 mol%, and at a temperature of -78 ° C. to 120 ° C. A method of polymerization is preferred.
  • a Lewis acid catalyst is preferably used as the catalyst, and a Lewis base compound is preferably used as the base added as a co-catalyst. Further, it is preferable that the equipment used for polymerization be dried at 200° C. for 2 hours or more immediately before use, and then immediately cooled under a nitrogen atmosphere to remove moisture on the surface after being taken out of the dryer or the like.
  • an initiator generally used in cationic polymerization or living cationic polymerization is selected, and a Lewis acid catalyst is preferably selected from the viewpoint of ease of polymerization control.
  • the Lewis acid catalyst is a compound consisting of a metal ion (acid) and a ligand (base), and can be used without any particular restriction as long as it can accept an electron pair.
  • metal fluorides or complexes thereof are preferable, and in particular B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Divalent to hexavalent metal fluorides such as Ti, W, Zn, Fe and V or complexes thereof are preferred.
  • ether complex of boron trifluoride is most preferably used.
  • examples of the ether of the ether complex include diethyl ether, dimethyl ether, dibutyl ether, and the like. Boron trifluoride diethyl ether complex is particularly preferred because it is easily available and inexpensive.
  • the catalyst is preferably used in a molar ratio of 0.0001 to 10, more preferably 0.001 to 1, and still more preferably 0.001 to 0, based on the total amount of monomers. .1. If the molar ratio is 10 or less, the polymerization rate will not become too high and polymerization control such as molecular weight distribution will become easy. Moreover, when it is 0.0001 or more, a sufficient polymerization rate is ensured and the time required for polymerization is reduced, which leads to cost reduction and is preferable for industrial implementation.
  • Lewis base compounds are used as the added base.
  • the Lewis base compound include monoester compounds, diester compounds, thioester compounds, thioether compounds, ketone compounds, ether compounds, and phosphine compounds.
  • An appropriate Lewis base compound is selected depending on the initiator (catalyst) used for polymerization, but for example, when boron trifluoride diethyl ether complex is used as a catalyst, monoester compounds and diester compounds are preferably used.
  • Ru Specific examples include acetate esters such as butyl acetate, and diesters such as dimethyl adipate and diethyl malonate.
  • Lewis base compounds can be used alone or in combination of two or more.
  • Lewis base compounds act as monomers that also act as chain transfer agents by coordinating to the Lewis acid catalyst, which is the counter anion, and controlling the interaction between the carbocation, which is the active species, and the counter anion, during the polymerization reaction. Adjust the relative frequency of responses between.
  • the carbocation terminal which is an active species, interacts with the Lewis base compound, so side reactions such as the carbocation terminal acting on other molecular chains are suppressed, and the molecular weight Distribution can be controlled.
  • the Lewis base compound is added at a molar ratio of preferably 0.1 to 100, more preferably 1 to 100, particularly preferably 5 to 50, based on the amount of the catalyst.
  • the polymerization rate can be maintained appropriately, the side reactions mentioned above can be suppressed, and a polyfunctional vinyl aromatic copolymer with a monomodal molecular weight distribution can be obtained.
  • a solvent can be added to the polymerization, if desired.
  • the solvent is a compound that does not inhibit polymerization and dissolves the catalyst, co-catalyst, and monomer components to form a homogeneous solution.
  • Particularly preferred are toluene, xylene, n-hexane, cyclohexane, methylcyclohexane or ethylcyclohexane, and acetonitrile.
  • the amount of the solvent to be used is determined by considering the viscosity of the obtained polymerization solution and the ease of heat removal, so that the monomer component in the polymerization solution is 1 vol% to 90 vol%, preferably 1 vol% to 80 vol%, particularly preferably 1 vol%. % to 60 vol%. If this concentration is 1 vol% or more, it will ensure sufficient polymerization efficiency and lead to cost reduction, and if it is 90 vol% or less, the molecular weight and molecular weight distribution of the polyfunctional vinyl aromatic copolymer to be produced will be reduced, and the prepreg This leads to the suppression of voids and the improvement of the interlayer peel strength and moldability of the laminate.
  • the polymerization temperature is selected depending on the catalyst and solvent used, but from the viewpoint of industrial feasibility, it is preferably -20°C to 120°C, more preferably 30°C to 120°C, particularly preferably 40°C to 120°C. .
  • the polymerization temperature is 120° C. or lower, the selectivity of the reaction is improved, a sharper molecular weight distribution can be obtained, and the generation of gel can be suppressed. If the temperature is -78°C or higher, sufficient catalytic activity can be ensured and polymerization efficiency can be improved.
  • the method for recovering the polyfunctional vinyl aromatic copolymer is not particularly limited, and for example, commonly used methods such as heating concentration, steam stripping, and precipitation in a poor solvent may be used. From the viewpoint of removing compounds used in polymerization and recovery, such as catalysts, co-catalysts, and solvents, from the copolymer and reducing the residual amount, a method of repeating precipitation in a poor solvent multiple times is preferred.
  • the curable resin composition of the present disclosure contains a polyfunctional vinyl aromatic copolymer and is selected from the group consisting of a curable reactive compound, a curable reactive resin, a thermoplastic resin, and a radical polymerization initiator. contains at least one. If desired, it may further contain an initiator such as a radical polymerization initiator, a flame retardant, a silica filler, a solvent, and the like.
  • an initiator such as a radical polymerization initiator, a flame retardant, a silica filler, a solvent, and the like.
  • curable reactive compound refers to a low molecular weight compound that functions as a crosslinking agent when curing a curable resin composition, and specifically refers to a compound with a molecular weight of less than 300.
  • curable reactive compound trialkenyl isocyanurate and/or trialkenyl cyanurate (hereinafter abbreviated as “trialkenyl isocyanurate/cyanurate”) is preferred from the viewpoint of ease of handling since it is liquid at room temperature.
  • trialkenyl isocyanurate compounds include triallyl isocyanurate (TAIC); examples of trialkenyl cyanurate compounds include triallyl cyanurate (TAC); It is more preferable because it further improves the compatibility of any of the plastic resins and further improves the heat resistance and interlayer peel strength of the laminate.
  • TAIC triallyl isocyanurate
  • TAC triallyl cyanurate
  • the amount of trialkenyl isocyanurate/cyanurate in the curable resin composition is preferably 2% by mass to 20% by mass based on the total weight of components other than the solvent.
  • the blending amount of trialkenyl isocyanurate/cyanurate is determined from the viewpoint of compatibility with other components, or molded bodies of resin compositions, prepregs containing resin compositions, laminates of multiple prepregs, laminates of prepregs and substrates, etc. From the viewpoint of reducing the dielectric loss tangent, improving heat resistance, and good appearance, the content is more preferably 2% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass.
  • a general crosslinking agent may be added to the curable reactive compound as long as the properties are not impaired.
  • a polyfunctional compound having two or more methacrylic groups in the molecule Methacrylate compounds, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene, divinylbenzene having vinylbenzyl groups in the molecule (however, the above-mentioned Examples include vinylbenzyl compounds such as (excluding addition as a copolymerizable monomer in component (b)), polyfunctional maleimide compounds having two or more maleimide groups in the molecule such as 4,4'-bismaleimide diphenylmethane, etc. .
  • curable reactive resin refers to a polymeric material other than a polyfunctional vinyl aromatic copolymer that can function as a crosslinking agent when curing a curable resin composition. refers to compounds with a molecular weight of 300 or more.
  • polyphenylene ether hereinafter abbreviated as "PPE"
  • PPE polyphenylene ether
  • PPE contains phenylene ether units as repeating structural units. The phenylene group in the phenylene ether unit may or may not have a substituent.
  • PPE as a curable reactive resin includes dimers, trimers, oligomers, and polymers.
  • the curable reactive resin may be blended as a main material in the curable resin composition, thereby making it possible to obtain a cured product with excellent strength.
  • “Incorporated as a main ingredient” means that it occupies the largest mass % among the components contained in the curable resin composition.
  • PPE may also contain other structural units other than phenylene ether units.
  • the amount of other structural units is typically 30 mol% or less, 25 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less, or 5 mol% or less based on the total number of unit structures. However, the amount of other structural units may exceed 30 mol% based on the total number of unit structures, as long as it does not impede the effects of the present disclosure.
  • PPE examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6-phenylene ether).
  • -phenyl-1,4-phenylene ether poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g. 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.);
  • PPE copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols; and poly(2,6- A linear structure or Examples include PPE having a branched structure.
  • PPE in which the terminal hydroxyl group of these PPEs is substituted with a functional group containing a carbon-carbon double bond may also be mentioned.
  • functional groups having a carbon-carbon double bond include vinyl group, allyl group, isopropenyl group, 1-butenyl group, 1-pentenyl group, p-vinylphenyl group, p-isopropenylphenyl group, m -vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group , o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinyl
  • the number average molecular weight of the PPE is preferably 1,000 to 5,000.
  • the number average molecular weight of the low molecular weight PPE is preferably from 1,000 to 4,000, or from 1,500 to 3,000.
  • the PPE contained in the curable reactive resin may be one type or a combination of two or more PPEs having a number average molecular weight of 1,000 to 5,000.
  • the amount of PPE blended in the curable resin composition is 50% by mass to 90% by mass based on the total weight of components other than the solvent.
  • the amount of PPE to be blended is determined from the viewpoint of compatibility with other components, reduction of dielectric loss tangent, and heat resistance of cured products of curable resin compositions, prepregs, laminates of multiple prepregs, laminates of prepregs and substrates, etc. From the viewpoint of improvement in color and good appearance, the content is preferably 50% by mass to 80% by mass, more preferably 50% by mass to 70% by mass.
  • radical polymerization initiator examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di(t-butyl peroxide).
  • a radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition.
  • 2,5-dimethyl-2,5-di(t-butyl peroxide) is preferred from the viewpoint of being able to provide a cured product with excellent heat resistance and mechanical properties, as well as low dielectric constant and low dielectric loss tangent.
  • Preferred are oxy)hexyne-3, di(2-t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
  • the 1-minute half-life temperature of the radical polymerization initiator is preferably 155°C to 185°C, or 160°C to 180°C, or 165°C to 175°C.
  • the 1-minute half-life temperature is the temperature at which it takes 1 minute for the radical polymerization initiator to decompose and the amount of active oxygen to be halved.
  • the 1-minute half-life temperature is determined by dissolving a radical polymerization initiator in a radical-inactive solvent such as benzene to a concentration of 0.05 mol/L to 0.1 mol/L, and preparing a radical polymerization initiator solution. This is a value confirmed by a method of thermally decomposing the compound in a nitrogen atmosphere.
  • the 1-minute half-life temperature of the radical polymerization initiator is 155°C or higher, when the resin composition is subjected to heating and pressure molding, the reaction with the crosslinking agent can be started after sufficiently melting the PPE. They tend to be good at sex.
  • the 1-minute half-life temperature of the radical polymerization initiator is 185°C or lower, the decomposition rate of the radical polymerization initiator is sufficient under normal heating and pressure molding conditions (for example, maximum temperature of 200°C). Since the crosslinking reaction with the crosslinking agent can proceed efficiently and slowly, it is possible to form a cured product having good electrical properties (particularly dielectric loss tangent).
  • t-hexylperoxyisopropyl monocarbonate 155.0°C (the 1-minute half-life temperature in parentheses is below)
  • t-butylperoxy-3,5,5-trimethylhexanoate (166.0°C)
  • t-butylperoxylaurate 159.4°C
  • t-butylperoxyisopropyl monocarbonate 158.8°C
  • t-butylperoxy 2-ethylhexyl monocarbonate (161.4°C
  • t-hexylperoxybenzoate (160.3°C), 2,5-dimethyl-2,5-di(benzoylperoxy) ) Hexane (158.2°C), t-butylperoxyacetate (159.9°C), 2,2-di-(t-butylperoxy)butane (159.
  • the content of the radical polymerization initiator is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the curable resin composition of 100% by mass, from the viewpoint of increasing the reaction rate. It is preferably 1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, from the viewpoint that the dielectric constant and dielectric loss tangent of the obtained cured product can be kept low. It is 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less.
  • the curable resin composition contains a flame retardant.
  • flame retardants include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylene bistetrabromophthalimide, etc. aromatic bromine compounds; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate; These flame retardants may be used alone or in combination of two or more.
  • the flame retardant is preferably decabromodiphenylethane from the viewpoint that the curable resin composition has a low dielectric constant and a low dielectric loss tangent when cured.
  • the content of the flame retardant is not particularly limited, but from the viewpoint of maintaining flame retardancy at the UL standard 94V-0 level, preferably 5 parts by mass or more, based on a total of 100 parts by mass of the curable resin composition. More preferably, it is 10 parts by mass or more, and still more preferably 15 parts by mass or more.
  • the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less. be.
  • the curable resin composition may contain a filler.
  • the filler may include silica filler.
  • silica filler either natural silica or synthetic silica can be used, and examples thereof include fused silica, amorphous silica, Aerosil, and hollow silica.
  • the content of the silica filler can be 10 to 100 parts by mass based on a total of 100 parts by mass of the PPE and all components that can be used as crosslinking agents.
  • the silica filler may be surface-treated using a silane coupling agent or the like.
  • the curable resin composition may further contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, and a lubricant.
  • additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, and a lubricant.
  • the resin composition varnish of the present disclosure contains an organic solvent and the curable resin composition of the present disclosure dissolved in the organic solvent.
  • the resin composition varnish can have suitable fluidity when impregnated into glass cloth. In the prepreg manufacturing process, it is preferable to impregnate glass cloth with a resin composition varnish and then dry and remove the solvent using a hot air dryer or the like.
  • the solid components in the resin composition varnish may be dissolved or dispersed in the varnish.
  • the amount of solvent may be adjusted as appropriate so that the fluidity of the resin composition varnish falls within a suitable range. For example, the amount of solvent in the resin composition varnish may range from 20% by mass to 80% by mass, or It may be from 40% to 60% by weight, or from 40% to 60% by weight.
  • aromatic compounds such as toluene and xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, and chloroform are preferable. These solvents may be used alone or in combination of two or more.
  • the solvent is preferably an aromatic compound such as toluene, such as a mixed solvent of toluene and methyl ethyl ketone, a mixed solvent of toluene and cyclohexanone, and a mixed solvent of toluene and cyclohexanone.
  • a mixed solvent of toluene and cyclopentanone is preferred.
  • the resin composition of the present disclosure is preferably dissolved in a solvent containing toluene alone, and has excellent impregnating properties into a substrate, so a solvent containing toluene alone is also preferable as the solvent.
  • the curable composite material (also referred to as "prepreg") of the present disclosure includes a curable resin composition and a base material, where the base material constitutes 1% to 99% by mass based on the total mass of the curable composite material. do.
  • the base material include glass cloth formed from E glass fiber, L glass fiber, and S glass fiber, and organic fiber cloth formed from aramid resin fiber and the like.
  • the method for manufacturing the curable composite material include a method in which a base material is impregnated with the resin composition varnish of the present disclosure described above and the solvent is dried and removed.
  • the metal-clad laminate of the present disclosure includes a layer (uncured) of the curable composite material of the present disclosure and a metal foil layer.
  • the metal-clad laminate of the present disclosure can be manufactured by laminating a layer of the curable composite material of the present disclosure and a metal foil layer.
  • the curable composite material to be combined with the metal foil may be one or more sheets, and depending on the application, the curable composite material can be processed into a metal-clad laminate by laminating the metal foil on one or both sides.
  • a cured product obtained by curing the curable resin composition of the present disclosure is also provided.
  • the cured product of the present disclosure has excellent dielectric properties and heat resistance, has few voids, and has a good appearance.
  • cured composite material examples include a cured composite material obtained by curing the curable composite material (prepreg) of the present disclosure described above. Curing can be performed by heating at the curing temperature of the resin composition for a predetermined period of time.
  • a laminate plate (laminate) can be provided by laminating a plurality of curable composite materials (prepregs) and curing them. More specifically, by laminating a plurality of curable composite materials (prepregs) and curing them, a laminate having a plurality of layers of the cured composite material of the present disclosure can be provided.
  • the curable composite material (prepreg) may be laminated with other layers and cured, if desired. More specifically, by curing a metal-clad laminate in which a layer of the curable composite material of the present disclosure and a metal foil layer are laminated, a layer of the cured composite material of the present disclosure and a metal foil layer is formed.
  • a hardened metal clad laminate can be provided.
  • the dielectric loss tangent of the hardened metal-clad laminate is preferably less than 0.0033, more preferably 0.0031 or less, when measured at 10 GHz by the method described in the Examples.
  • the cured metal-clad laminate preferably has a form in which a layer of a cured product (cured composite material) of a curable composite material (prepreg) and a metal foil layer are laminated and in close contact, and is used as a material for electronic circuit boards.
  • a layer of a cured product (cured composite material) of a curable composite material (prepreg) and a metal foil layer are laminated and in close contact, and is used as a material for electronic circuit boards.
  • the metal foil include aluminum foil and copper foil, and among these, copper foil is preferred because it has low electrical resistance.
  • One particularly preferred application for hardened metal clad laminates is printed wiring boards. In the printed wiring board, it is preferable that at least a portion of the metal foil is removed from the cured metal-clad laminate.
  • a printed wiring board is a metal-clad laminate with a portion of the metal foil removed.
  • a printed wiring board can typically be formed using the above-described curable composite material (prepreg) of the present disclosure by a method of pressurizing and heating molding.
  • the printed wiring board has excellent heat resistance and electrical properties (low dielectric constant and low dielectric loss tangent), and also has excellent resistance to environmental changes. It is possible to suppress fluctuations in electrical properties, and furthermore, it has excellent insulation reliability and mechanical properties.
  • the resin-coated metal foil includes a metal foil and a film obtained by curing the curable resin composition of the present disclosure on at least one or both sides of the metal foil.
  • the metal foil include aluminum foil and copper foil, and among these, copper foil is preferred because it has low electrical resistance. It can be created by vacuum pressing the uncured film and metal foil together.
  • Example 2 Copolymers were synthesized in the same manner as in Example 1, except that divinylbenzenes having different m-isomer ratios were used as monomers.
  • Example 9 8.3 mol of n-propyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 850 g), 7.2 mol of styrene (manufactured by Tokyo Chemical Industry Co., Ltd., 750 g), 0.9 mol of 4-n-octylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.9 mol (111 g) of divinylbenzene (manufactured by Kogyo Co., Ltd., 195 g) and having an m-isomer ratio of 60 mol % was charged into a 3 L flask.
  • boron trifluoride diethyl ether complex manufactured by Tokyo Chemical Industry Co., Ltd.
  • a cocatalyst n-propyl acetate
  • a monovinyl aromatic compound n-propyl acetate
  • a monovinyl aromatic compound n-propyl acetate
  • a monovinyl aromatic compound n-propyl acetate
  • a monovinyl aromatic compound n-propyl acetate
  • an alkylstyrene a divinyl aromatic compound
  • a catalyst diethyl ether complex of boron trifluoride
  • Example 10 to 14 A copolymer was synthesized in the same manner as in Example 1, except that the monomer ratios of styrene, 4-n-octylstyrene, and divinylbenzene were different.
  • Example 15 to 21 A copolymer was synthesized in the same manner as in Example 1, except that the type of 4-n-alkylstyrene used as the comonomer was different. Note that 4-n-alkylstyrene was synthesized in-house.
  • Example 22 A copolymer was synthesized in the same manner as in Example 9, except that the alkylstyrene used as the comonomer was t-butylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • Copolymers were synthesized in the same manner as in Example 1, except that divinylbenzenes having different m-isomer ratios were used as monomers.
  • Table 4 shows the synthesis results of the comparative example and the evaluation results of the evaluation method below.
  • a curable resin composition was prepared by mixing the following materials.
  • curable reactive resin (curable reactive resin) - PPE modified with a terminal methacrylic group (product name "SA9000”, manufactured by Sabic Innovative Plastics, Mn: 2756, number of terminal functional groups per molecule: 2)
  • a laminate of 50 mm x 80 mm was visually evaluated for the presence or absence of fading on the exterior of the laminate, which indicates a portion where the glass cloth yarn bundle was not impregnated with resin. Specifically, the laminate was illuminated with a penlight at an angle of 30° and visually observed from an angle of 45° to confirm the presence or absence of fading.
  • the dielectric loss tangent of the laminate at 10 GHz was measured using a cavity resonance method.
  • the measurement was performed using a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Denshi Applied Development Co., Ltd. as measurement devices.
  • a test piece used for measuring the glass transition temperature (Tg) was prepared by cutting the laminate into a piece having a width of 3.0 mm and a length of 25 mm. The obtained test piece was set in a TMA (thermo-mechanical analyzer), heated to 220°C at a heating rate of 10°C/min under a nitrogen stream, and further heat-treated at 220°C for 20 minutes to determine the remaining molding. Removed distortion. After the test piece was allowed to cool to room temperature, it was fixed on the chuck of a TMA measuring device, scan measurement was performed from 30°C to 320°C at a heating rate of 10°C/min under a nitrogen stream, and Tg was determined by the tangential method.
  • TMA thermo-mechanical analyzer
  • the laminate was cut into a size of 50 mm x 50 mm and placed in a pressure cooker at 121° C. and saturated vapor pressure for 10 hours. The laminate was taken out, and after wiping off moisture on the surface, it was immersed in a 288° C. solder bath for 20 seconds. The degree of swelling of the laminate after immersion was evaluated according to the following evaluation criteria. AA: No bulges with a diameter of 2 mm or more occurred.A: No bulges with a diameter of 3 mm or more occurred.B: 1 to 3 bulges with a diameter of 3 mm or more, and no bulges with a diameter of 5 mm or more.C. : 4 or more bulges with a diameter of 3 mm or more, or 1 or more bulges with a diameter of 5 mm or more.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Un but de la présente divulgation est de fournir : un copolymère aromatique vinylique multifonctionnel qui permet d'obtenir un préimprégné qui présente d'excellentes caractéristiques diélectriques et une excellente résistance à la chaleur, tout en ayant moins de vides, un stratifié qui a un bon aspect et une résistance au pelage intercouche élevée, et similaire ; et une composition de résine durcissable et similaire qui contiennent ce copolymère aromatique vinylique multifonctionnel. La présente divulgation concerne un copolymère aromatique vinylique multifonctionnel qui a une unité structurale dérivée d'un composé aromatique divinylique et une unité structurale dérivée d'un composé aromatique monovinylique. La proportion de formes m du composé aromatique divinylique est de 60 % en moles ou plus ; et la polydispersité (Mw/Mn) exprimée par le rapport de la masse moléculaire moyenne en poids à la masse moléculaire moyenne en nombre du copolymère aromatique vinylique multifonctionnel est de 1 à 2,5.
PCT/JP2023/011253 2022-03-28 2023-03-22 Copolymère aromatique vinylique multifonctionnel WO2023189949A1 (fr)

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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
WO2020262371A1 (fr) * 2019-06-25 2020-12-30 日鉄ケミカル＆マテリアル株式会社 Copolymère vinylaromatique modifié, son procédé de production, copolymère de diène conjugué modifié obtenu à partir de celui-ci et sa composition, objet en caoutchouc réticulé et élément de pneu

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