WO2024162189A1 - 化合物、硬化性樹脂組成物およびその硬化物 - Google Patents

化合物、硬化性樹脂組成物およびその硬化物 Download PDF

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WO2024162189A1
WO2024162189A1 PCT/JP2024/002335 JP2024002335W WO2024162189A1 WO 2024162189 A1 WO2024162189 A1 WO 2024162189A1 JP 2024002335 W JP2024002335 W JP 2024002335W WO 2024162189 A1 WO2024162189 A1 WO 2024162189A1
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compound
acid
resin composition
represent
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French (fr)
Japanese (ja)
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隆行 遠島
昌典 橋本
政隆 中西
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Nippon Kayaku 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a compound having a specific structure, a curable resin composition and a cured product thereof, which are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards and build-up laminates, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.
  • the frequency used will become higher, but in order to realize high-speed communication using high frequencies, it is important to reduce transmission loss, and further low dielectric properties (low dielectric constant and low dielectric loss tangent) of the board material will be required.
  • the transmission loss occurring on the printed circuit board is due to conductor loss and dielectric loss.
  • the dielectric loss ⁇ D is proportional to the square root of the relative dielectric constant ⁇ and the dielectric loss tangent tan ⁇ of the dielectric, so it can be said that reducing the dielectric loss tangent, which has a higher contribution rate than the relative dielectric constant, is effective in reducing the dielectric loss.
  • Low-dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they are poor in moldability compared to thermosetting resins. In light of this, the development of thermosetting resins with excellent low dielectric properties is desired.
  • Patent Document 1 proposes a thermosetting resin composition containing an imide compound having a maleimide group and a phenol aralkyl resin having an aliphatic unsaturated bond.
  • Patent Document 2 discloses an allyl ether-modified biphenyl aralkyl novolac resin in which an allyl group is added to a phenolic hydroxyl group.
  • the present invention was made in consideration of these circumstances, and aims to provide a compound with excellent low dielectric properties, a curable resin composition, and a cured product thereof.
  • the present invention relates to the following [1] to [11]. Note that in this application, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limits are included.
  • H-AB hydrogenated block copolymer
  • R1 and R2 each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • p represents 1 to 5
  • j, k, l, m, and n each represent the average number of repeats and represent a real number from 1 to 10000.
  • the order of the repeat units bounded by k and l, or j, m, and n, is not limited, and the bonding style may be any of alternating, block, and random.
  • j, k, l, m, and n are the average number of repeats and represent real numbers from 1 to 10,000.
  • the order of each repeat unit grouped by k and l, or j, m, and n, is not limited, and the bonding style may be alternating, block, or random.
  • a curable resin composition comprising the compound according to any one of items [1] to [6] above.
  • the curable resin composition according to the above item [7] or [8] further contains at least one selected from the group consisting of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, a cyanate ester resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof.
  • the present invention makes it possible to provide a compound with excellent low dielectric properties, a curable resin composition, and a cured product thereof.
  • the compound of the present invention is obtained by reacting an acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB), which is an acid-modified product of a hydrogenated block copolymer (H-AB) consisting of block units (A) of a polymer made of a styrene-based monomer and block units (B) of a polymer made of a conjugated diene compound, with allylamine or allylamine hydrochloride.
  • AH-AB acid-modified hydrogenated thermoplastic styrene-based elastomer
  • the block unit (A) of the polymer made of a styrene-based monomer preferably has a structure represented by the following formula (a):
  • R1 and R2 are each preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. If the number of carbon atoms is greater than 5, the dielectric tangent may deteriorate due to molecular vibration, and heat resistance may decrease.
  • p is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
  • q is the average number of repetitions and represents a real number of 1 to 10,000, and q is preferably 1 to 7,500, more preferably 1 to 5,000, and even more preferably 1 to 3,000.
  • the block unit (B) of the polymer made of a conjugated diene compound is obtained by polymerizing at least one diene compound selected from linear conjugated dienes such as 1,3-butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. From the viewpoint of availability of raw materials, among the linear conjugated dienes, 1,3-butadiene, isoprene, and farnesene are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is the most preferred.
  • linear conjugated dienes such as 1,3-butadiene, isoprene, farnesene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.
  • 1,3-butadiene, isoprene, and farnesene are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-but
  • H-AB hydrogenated block copolymer
  • R 1 , R 2 and p are the same as those in formula (a).
  • j, k, l, m and n are the average number of repeats and represent real numbers from 1 to 10,000, preferably from 1 to 9,000, and more preferably from 1 to 8,000.
  • the order of the repeat units bounded by k and l, or j, m and n, is not limited, and the bonding style may be any of alternating, block or random.
  • a compound represented by the following formula (1-1) is preferred.
  • the values and preferred ranges of j, k, l, m, and n are the same as those in formula (1).
  • the order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be alternating, block, or random.
  • H-AB hydrogenated block copolymer
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • the compound represented by formula (1) does not have a polar group, nor does it have an unsaturated bond derived from an aliphatic hydrocarbon. Therefore, even if it is exposed to temperatures of 125°C or higher, which is the temperature at which semiconductors are guaranteed to operate, it is not easily oxidized, and the oxygen contained in the polar group is not easily incorporated into the skeleton. Therefore, deterioration of the dielectric properties after high-temperature storage tests can be reduced, and it also has excellent low water absorption properties.
  • AH-AB acid-modified hydrogenated thermoplastic styrene-based elastomer
  • R1 , R2 , p, j, k, l, m, and n in formula (2) are the same as those in formula (1).
  • the order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.
  • the most preferred embodiment of the acid-modified hydrogenated thermoplastic styrene-based elastomer is an acid-modified hydrogenated styrene-butadiene-styrene block copolymer (SEBS).
  • the compound represented by the formula (2) can be obtained by reacting the compound represented by the formula (1) with maleic anhydride in the presence of a radical polymerization initiator, or by reacting the compound represented by the formula (1) with maleic acid in the presence of a radical polymerization initiator, followed by dehydration.
  • the compound represented by the formula (2-1) can be obtained by reacting the compound represented by the formula (1-1) with maleic anhydride in the presence of a radical polymerization initiator, or by reacting the compound represented by the formula (1-1) with maleic acid in the presence of a radical polymerization initiator, followed by dehydration.
  • the content of styrene-derived structural units in the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) may be 5-80% by mass, 5-70% by mass, 10-70% by mass, or 10-50% by mass, from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric tangent), adhesion to conductors, heat resistance, glass transition temperature, and thermal expansion coefficient.
  • the melt flow rate (MFR) of the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) is not particularly limited, but may be 0.1-20 g/10 min or 0.5-15 g/10 min under measurement conditions of 230°C and a load of 2.16 kgf (21.2 N).
  • AH-AB acid-modified hydrogenated thermoplastic styrene-based elastomers
  • the preferred structure of the compound of the present invention obtained by reacting an acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) with allylamine or allylamine hydrochloride is represented by the following formula (3).
  • R1 , R2 , p, j, k, l, m, and n in formula (3) are the same as those in formula (1).
  • the order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.
  • a compound represented by the following formula (3-1) is preferred.
  • the values and preferred ranges of j, k, l, m, and n in formula (3-1) are the same as those in formula (1).
  • the order of the repeating units bounded by k and l, or j, m, and n, is not limited, and the bonding pattern may be any of alternating, block, and random.
  • the most preferred embodiment of the compound of the present invention is a compound having a structure derived from an acid-modified hydrogenated styrene-butadiene-styrene block copolymer (SEBS).
  • SEBS acid-modified hydrogenated styrene-butadiene-styrene block copolymer
  • the reaction of the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) with allylamine or allylamine hydrochloride may be carried out by any known imidization reaction method, for example, by reacting the acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB) with allylamine or allylamine hydrochloride in a non-water-soluble aromatic hydrocarbon solvent such as toluene, xylene, or mesitylene while removing the generated water from the system by azeotropy.
  • a non-water-soluble aromatic hydrocarbon solvent such as toluene, xylene, or mesitylene
  • a base catalyst such as triethylamine or an acid catalyst such as activated clay, paratoluenesulfonic acid, methanesulfonic acid, or hydrochloric acid may be used.
  • An aprotic polar solvent such as N-methyl-2-pyrrolidone or N,N-dimethylformamide may be used in combination to dissolve the amic acid and promote the imidization process.
  • Allylamine or allylamine hydrochloride is preferably used in an amount of 0.5 to 1.5 mol per mol of acid anhydride structure, more preferably 0.8 to 1.2 mol, and most preferably 0.9 to 1.1 mol. Outside the above range, the dielectric properties may deteriorate due to the polar groups of the remaining raw materials.
  • the reaction is carried out at 80 to 200°C, preferably 100 to 180°C, for 0.5 to 20 hours.
  • the number average molecular weight of the compound of the present invention is preferably 10,000 or more and less than 1,000,000, more preferably 20,000 or more and less than 500,000, and even more preferably 30,000 or more and less than 250,000. If it is less than 10,000, there is a risk that the heat resistance in the solder reflow process will be impaired. If it is 1,000,000 or more, there is a risk that the solvent solubility will be impaired or that the compound will not be sufficiently compatible with other thermosetting resin components.
  • the curable resin composition of the present invention can be used by mixing it with the various materials shown below in addition to the compound of the present invention.
  • the curable resin composition of the present invention can also improve the curability by adding a polymerization initiator.
  • the polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples of the polymerization initiator include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator having curability and moderate stability.
  • the radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and starts a chain polymerization reaction.
  • radical polymerization initiators examples include organic peroxides, azo compounds, and benzopinacoles, and it is preferable to use an organic peroxide because it has little effect on curing temperature control, outgassing suppression, and electrical properties of decomposition products.
  • organic peroxides include, for example, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, ⁇ -cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxypivalate.
  • ketone peroxides such as
  • peroxycarbonate examples include, but are not limited to, alkyl peresters such as peroxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate, peroxycarbonates such as di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropylcarbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyoctoate, and lauroyl peroxide.
  • alkyl peresters such as peroxy-2-ethylhexanoate, t-amylperoxy-3,5,5-
  • ketone peroxides diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, with dialkyl peroxides being more preferred.
  • azo compounds examples include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. Furthermore, these may be used alone or in combination.
  • the amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 parts by mass, there is a risk that the molecular weight will not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, there is a risk that the dielectric properties such as the dielectric constant and dielectric loss tangent will be impaired.
  • the curable resin composition of the present invention can also have improved curability by adding a curing accelerator.
  • a curing accelerator an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.
  • anionic curing accelerators examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene; of which 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.
  • imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole
  • trialkylamines such as triethylamine and tributylamine
  • 4-dimethylaminopyridine benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)
  • phosphines such as triphenylphosphine
  • quaternary ammonium salts such as tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecanylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but are not limited to these. These may be used alone or in combination.
  • cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt may be a halogen, an organic acid ion, a hydroxide ion, or the like, but is not limited to organic acid ions and hydroxide ions); transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate ester (zinc octylphosphate, zinc stearylphosphate); but are not limited to these. These may be used alone or in combination.
  • quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and t
  • the amount of the curing accelerator used is 0.01 to 5.0 parts by mass per 100 parts by mass of the curable resin composition, as needed.
  • the curable resin composition of the present invention may contain an inorganic filler.
  • inorganic fillers include powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, and inorganic fillers obtained by making these into a spherical or crushed shape, but are not limited thereto. In addition, these may be used alone or in combination.
  • the inorganic filler When obtaining a curable resin composition for semiconductor encapsulation, the inorganic filler is used in an amount of preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition.
  • the inorganic filler When obtaining a curable resin composition for use as an interlayer insulating layer forming material, or as a substrate material such as a copper-clad laminate, prepreg, or RCC, the inorganic filler is used in an amount of preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.
  • the curable resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, it becomes easy to ensure fluidity, impregnation into glass cloth and the like is not impaired, and B-stage such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.
  • the polymerization inhibitor may be added when synthesizing the compound of the present invention, or after synthesis.
  • the amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the compound of the present invention.
  • polymerization inhibitors examples include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based. Furthermore, one type of polymerization inhibitor may be used, or multiple types may be used in combination. Of these, in the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors are preferred.
  • phenol-based polymerization inhibitors include, for example, monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; -t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butyl
  • sulfur-based polymerization inhibitors examples include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.
  • Examples of the phosphorus-based polymerization inhibitors include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of the phosphites
  • Examples of the above hindered amine-based polymerization inhibitors include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB Examples include, but are not limited to, LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc.
  • nitroso-based polymerization inhibitor examples include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and the ammonium salt of N-nitrosophenylhydroxyamine (cupferron). Of these, the ammonium salt of N-nitrosophenylhydroxyamine (cupferron) is preferred.
  • nitroxyl radical polymerization inhibitor examples include, but are not limited to, di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
  • the curable resin composition of the present invention may contain a flame retardant.
  • the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred.
  • the phosphorus-based flame retardant may be of a reactive type or an additive type.
  • phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylyleneyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyleneyl phosphate, 1,3-phenylene bis(dixylyleneyl phosphate), 1,4-phenylene bis(dixylyleneyl phosphate), and 4,4'-biphenyl(dixylyleneyl phosphate), phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus-containing epoxy compounds obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, and the like, but are not limited thereto.
  • phosphoric acid esters such as
  • phosphates, phosphanes, and phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate) and phosphorus-containing epoxy compounds being particularly preferred.
  • the content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.1 part by mass, there is a risk that the flame retardancy will be insufficient, and if it is more than 0.6 parts by mass, there is a risk that it will have a negative effect on the moisture absorption and dielectric properties of the cured product.
  • the curable resin composition of the present invention may contain a light stabilizer.
  • a light stabilizer a hindered amine light stabilizer, particularly HALS, etc.
  • HALS include reaction products of dibutylamine, 1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, reaction products of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ ], bis
  • the content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.001 parts by mass, it may be insufficient to achieve the light stabilizing effect, and if it is more than 0.1 parts by mass, it may have a negative effect on the moisture absorption and dielectric properties of the cured product.
  • the curable resin composition of the present invention may use a binder resin.
  • the binder resin include, but are not limited to, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, and silicone resins. These may be used alone or in combination.
  • the amount of binder resin used is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin composition, as needed.
  • the curable resin composition of the present invention may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
  • additives such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
  • the amount of additive is preferably 1 part by mass or less, and more preferably 0.7 parts by mass or less, per 100 parts by mass of the curable resin composition.
  • the curable resin composition of the present invention may further contain epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having ethylenic unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, etc., which may be used alone or in combination.
  • maleimide compounds polyphenylene ether compounds, compounds having ethylenic unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, and polyethylene and modified products thereof, in view of the balance of heat resistance, adhesion, and dielectric properties.
  • the brittleness of the cured product and adhesion to metals can be improved, and cracks in the package during solder reflow and during reliability tests such as thermal cycles can be suppressed.
  • the total amount of the above compounds used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass, relative to the compound of the present invention, unless otherwise specified.
  • the lower limit is preferably 0.1 times by mass or more, more preferably 0.25 times by mass or more, and even more preferably 0.5 times by mass or more.
  • epoxy resin Preferred examples of the epoxy resin are shown below, but the epoxy resin is not limited thereto.
  • the epoxy resin may be liquid or solid, and may be used alone or in combination.
  • liquid epoxy resins examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure.
  • solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and examples of such solid epoxy resins include naphthol type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.
  • HP4032H manufactured by DIC Corporation, naphthalene type epoxy resin
  • HP-4700 manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin
  • HP-4710 all manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin
  • N-690 manufactured by DIC Corporation, cresol novolac type epoxy resin
  • N-695" manufactured by DIC Corporation, cresol novolac type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200 manufactured by DIC Corporation, dicyclopentadiene type epoxy resin
  • HP-7200HH manufactured by DIC Corporation, dicyclopentad
  • epoxy resin "EXA-7311”, “EXA-7311-G3", “EXA-7311-G4", “EXA-7311-G4S”, "HP-6000” (all manufactured by DIC Corporation, naphthylene ether type epoxy resin), "EPPN-502H” (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L”, “NC-7300” (all manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H”, “NC-3000”, “NC-3000L”, “NC-3100” (all manufactured by Nippon Kayaku Co., Ltd., biphenyl ether type epoxy resin).
  • the active ester compound refers to a compound that contains at least one ester bond in the structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond.
  • the active ester compound include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, and are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound.
  • the hydroxy compound is preferably a phenol compound or a naphthol compound.
  • the active ester compound may be used alone or in combination of two or more types.
  • carboxylic acid compounds examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • Examples of the acid chlorides include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.
  • phenol compounds and naphthol compounds include, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described below.
  • dicyclopentadiene-type diphenol compounds refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of
  • active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compounds described in Example 2 of WO 2020/095829, and the compounds disclosed in WO 2020/059625.
  • active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred.
  • the dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
  • active ester compounds include, for example, "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000H-65TM”, “EXB-8000L-65TM”, and “EXB-8150-65T” (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and "phenolnoxamine” (manufactured by DIC Corporation).
  • active ester compounds containing acetylated volac examples include “DC808” (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolac include “YLH1026", “YLH1030", and “YLH1048” (manufactured by Mitsubishi Chemical Corporation), active ester curing agent that is an acetylated phenol novolac, and "EXB-9050L-62M” (manufactured by DIC Corporation) as an active ester curing agent containing phosphorus atoms.
  • the ratio ( ⁇ / ⁇ ) of the active ester equivalent ( ⁇ ) to the epoxy equivalent ( ⁇ ) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. Outside the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, which may cause deterioration of characteristics in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).
  • a phenolic resin is a compound having two or more phenolic hydroxyl groups in a molecule.
  • the phenolic resin include, but are not limited to, a reaction product of a phenol with an aldehyde, a reaction product of a phenol with a diene compound, a reaction product of a phenol with a ketone, a reaction product of a phenol with a substituted biphenyl, a reaction product of a phenol with a substituted phenyl, a reaction product of a bisphenol with an aldehyde, and the like. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto.
  • Phenol alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.
  • ⁇ Aldehydes > Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like.
  • ⁇ Diene Compound Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like.
  • ⁇ Ketones Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.
  • ⁇ Substituted biphenyls > 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, and the like.
  • ⁇ Substituted phenyls > 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene and the like.
  • the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure.
  • Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound having a styrene structure).
  • the number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. If the molecular weight is more than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which decreases the glass transition temperature of the cured product and tends to decrease the heat resistance of the cured product.
  • the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties.
  • the number average molecular weight here can be specifically measured using gel permeation chromatography, etc.
  • the polyphenylene ether compound may be one obtained by a polymerization reaction, or one obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. These may also be used as raw materials and reacted with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene, to impart radical polymerizability.
  • a compound having an ethylenically unsaturated bond such as methacryl chloride, acrylic chloride, or chloromethylstyrene
  • the polyphenylene ether compound obtained by the redistribution reaction may be obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction.
  • the polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain, and is therefore preferable in that it can maintain even higher heat resistance, and that functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond.
  • the polyphenylene ether compound obtained by the polymerization reaction is also preferable in that it exhibits excellent fluidity.
  • the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions.
  • the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, it is possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained polyphenylene ether compound.
  • poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as a high molecular weight polyphenylene ether compound that undergoes the redistribution reaction.
  • the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc., is preferably used. These may be used alone or in combination of two or more.
  • the amine resin is a compound having two or more amino groups in the molecule.
  • the amine resin include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolak (a reaction product of aniline and formalin), N-methylaniline novolak (a reaction product of N-methylaniline and formalin), orthoethylaniline novolak (a reaction product of orthoethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, and a reaction product obtained by reacting aniline and xylylene chloride.
  • aniline resin examples include, but are not limited to, the aniline resin disclosed in Japanese Patent No. 6429862, a reaction product of aniline and a substituted biphenyl (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), a reaction product of aniline and a substituted phenyl (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, a reaction product of aniline and diisopropenylbenzene, dimer diamine, etc. Furthermore, these may be used alone or in combination.
  • the compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.
  • Examples of the compound containing an ethylenically unsaturated bond include, but are not limited to, a reaction product of the phenol resin with an ethylenically unsaturated bond-containing halogen-based compound (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), a reaction product of an ethylenically unsaturated bond-containing phenol (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with a halogen-based compound (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), a reaction
  • An isocyanate resin is a compound having two or more isocyanate groups in the molecule.
  • the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biure
  • polyamide resin examples include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymers of lactam compounds. These may be used alone or in combination. Specific examples of the above-mentioned raw materials are given below, but the raw materials are not limited thereto.
  • ⁇ Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, and 4,4'-dicarboxydiphenyl sulfide.
  • ⁇ Acid chloride Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride, and the like.
  • ⁇ Lactam > ⁇ -caprolactam, ⁇ -undecanelactam, ⁇ -laurolactam, and the like.
  • polyimide resin examples include, but are not limited to, reaction products of the diamines and the tetracarboxylic dianhydrides shown below. These may be used alone or in combination.
  • the curable resin composition of the present invention may contain a maleimide compound.
  • a maleimide compound is a compound having one or more maleimide groups in the molecule.
  • the maleimide compound include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), and Xylox type maleimide compounds (anilix).
  • maleimide manufactured by Mitsui Chemicals Fine Co., Ltd.
  • biphenylaralkyl-type maleimide compound solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compound described in WO 2020/054601 A), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or WO 2020/217679, MATERIAL STAGE Vol. 18, No. 12 2019 ⁇ Continued Epoxy Resin CAS Number Story - Hardener CAS Number Memorandum No. 31 Bismaleimide (1)'' and MATERIAL STAGE Vol. 19, No.
  • maleimide compounds include, but are not limited to, the maleimide compounds described in "Epoxy Resin CAS Number Story Continued - Hardener CAS Number Memorandum No. 32 Bismaleimide (2)" in 2019. These compounds may be used alone or in combination.
  • the cyanate ester resin is a cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide, and specific examples thereof include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopent
  • the cyanate ester compound is particularly preferred as the cyanate ester compound because it has low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
  • the cyanate ester resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, if necessary, to trimerize the cyanate group to form a sym-triazine ring.
  • the catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the cyanate ester resin and curable resin composition.
  • polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule.
  • the unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation.
  • Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, and the like. These may be used alone or in combination.
  • polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties.
  • styrene-butadiene rubber examples include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Corporation), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and examples of polybutadiene include B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.), and the like.
  • the molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10,000 in weight average molecular weight, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000.
  • the amount of volatilization is large, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, the compatibility with other curable resins is deteriorated.
  • compounds containing heteroatoms such as oxygen and nitrogen such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity.
  • the compound of the present invention is excellent in compatibility with materials having low polarity and low dielectric properties and compounds composed only of hydrocarbons, due to the fact that the compound itself does not have a skeleton design in which heteroatoms such as oxygen and nitrogen are actively introduced.
  • Polystyrene and its modified products are polystyrene or compounds having a structure derived from polystyrene in the molecule.
  • examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene/ethylene-propylene-styrene block copolymer: Septon 4003,
  • block copolymer examples include, but are not limited to, SEEPS-OH (a styrene-ethylene/ethylene propylene-styrene block copolymer having a hydroxyl group at the end: SEPTON HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: SEPTON 5125, SEPTON 5127, manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: HYBRAR 7125F, HYBRAR 7311F, manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), SEPTON V9827 (manufactured by Kuraray Co.
  • Polystyrene and modified products thereof have higher heat resistance and are less susceptible to oxidative deterioration, so it is preferable that they do not have unsaturated bonds.
  • the weight average molecular weight of polystyrene and modified products thereof is not particularly limited as long as it is 10,000 or more, but if it is too large, the compatibility with not only polyphenylene ether compounds but also low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.
  • Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule.
  • Examples of polyethylene and modified products thereof include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, etc., but are not limited thereto.
  • ethylene-propylene-ethylidene norbornene copolymers and ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure may be used alone or in combination.
  • the weight-average molecular weight of polyethylene and modified products thereof is not particularly limited as long as it is 10,000 or more. However, if it is too large, compatibility with not only the polyphenylene ether compound but also low molecular weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components having a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.
  • the curable resin composition of the present invention can be obtained by preparing the above components in a prescribed ratio, pre-curing at 130-180°C for 30-500 seconds, and then post-curing at 150-200°C for 2-15 hours, allowing the curing reaction to proceed sufficiently to obtain the cured product of the present invention.
  • the components of the curable resin composition can also be uniformly dispersed or dissolved in a solvent, etc., and cured after removing the solvent.
  • the method for preparing the curable resin composition of the present invention is not particularly limited, but the components may be mixed uniformly or may be prepolymerized.
  • a mixture containing the compound of the present invention is prepolymerized by heating in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent.
  • amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, inorganic fillers, and other additives may be added to form a prepolymer.
  • the components may be mixed or prepolymerized using, for example, an extruder, kneader, rolls, etc. in the absence of a solvent, and a reaction kettle with a stirrer, etc. in the presence of a solvent.
  • the mixture is kneaded at a temperature in the range of 50 to 100°C using a device such as a kneader, roll, or planetary mixer to obtain a uniform resin composition.
  • the obtained resin composition is crushed and then molded into a cylindrical tablet using a molding machine such as a tablet machine, or into a granular powder or powder molded body, or these compositions can be melted on a surface support and molded into a sheet having a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition.
  • the obtained molded body is a non-sticky molded body at 0 to 20°C, and even if stored at -25 to 0°C for one week or more, the flowability and curability are hardly reduced.
  • the obtained molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.
  • the curable resin composition of the present invention can be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent.
  • the curable resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.
  • a varnish which can be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and dried by heating to obtain a prepreg, which can be hot-press molded to obtain a cured product of the curable resin composition of the present invention.
  • the solvent used in this case is in an amount that occupies 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of the present invention and the solvent. If the composition is in a liquid state, a cured product of the curable resin containing carbon fiber can be obtained as it is, for example, by the RTM method.
  • the curable resin composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility, etc., in the B-stage.
  • a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of the present invention as a varnish onto a release film, removing the solvent under heating, and then carrying out B-stage formation.
  • This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.
  • the curable resin composition of the present invention can be heated and melted to reduce the viscosity, and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg.
  • reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers
  • Specific examples include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, as well as inorganic fibers other than glass, and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), fully aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not limited to these.
  • the shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like.
  • plain weave, saddle weave, twill weave, and the like are known as ways of weaving woven fabrics, and these known methods can be appropriately selected and used depending on the intended use and performance.
  • woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like are preferably used.
  • the thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. Prepregs can also be obtained by impregnating reinforcing fibers with the varnish and drying them by heating.
  • a laminate can be manufactured using the prepreg.
  • the laminate is not particularly limited as long as it has one or more prepregs, and may have any other layer.
  • the manufacturing method of the laminate can be appropriately applied by a generally known method, and is not particularly limited. For example, when molding a metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used, and the prepregs are laminated together and heated and pressurized to obtain a laminate. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, and more preferably 120 to 270 ° C.
  • the pressure to be applied is not particularly limited, but if the pressure is too high, it is difficult to adjust the solid content of the resin of the laminate, and the quality is not stable, and if the pressure is too low, air bubbles and adhesion between the laminates are deteriorated, so that 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable.
  • the laminate of this embodiment can be suitably used as a metal foil-clad laminate described later by providing a layer made of metal foil. The prepreg is cut into a desired shape and laminated with copper foil or the like as necessary. The laminate is then heated and cured while applying pressure thereto by press molding, autoclave molding, sheet winding molding or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.
  • the curable resin composition of the present invention can also be made into a resin sheet.
  • a method for obtaining a resin sheet from the curable resin composition of the present invention includes, for example, applying the curable resin composition onto a support film (support), drying the composition, and forming a resin composition layer on the support film.
  • the curable resin composition of the present invention it is essential that the film softens under the lamination temperature conditions (70°C to 140°C) in the vacuum lamination method, and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes in the circuit board at the same time as laminating the circuit board, and it is preferable to mix the above-mentioned components so as to exhibit such characteristics.
  • the obtained resin sheet or circuit board (copper-clad laminate, etc.) is required to have a uniform appearance in order to exhibit a certain performance at any part without causing a phenomenon in which different characteristic values are locally exhibited due to phase separation, etc.
  • the through holes in the circuit board have a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is preferable to make it possible to fill them with resin within this range. If both sides of the circuit board are to be laminated, it is desirable to fill about half of the through holes.
  • a specific method for producing the resin sheet is to prepare a resin composition that has been varnished by blending an organic solvent, and then to apply the varnished resin composition to the surface of a support film (Y), and then to dry the organic solvent by heating or blowing hot air onto the resin composition to form a resin composition layer (X).
  • the organic solvents used here preferably include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. It is also preferable to use organic solvents in such a ratio that the non-volatile content is 30 to 60% by mass of the total.
  • the thickness of the resin composition layer (X) to be formed must be equal to or greater than the thickness of the conductor layer of the circuit board to which the resin composition layer (X) is laminated. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer (X) is preferably 10 to 100 ⁇ m.
  • the resin composition layer (X) in the present invention may be protected with a protective film, which will be described later. By protecting the resin composition layer (X) with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer (X) and to prevent scratches.
  • the support film and protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; polyimide; and even release paper and metal foils such as copper foil and aluminum foil.
  • the support film and protective film may be subjected to a mud treatment, corona treatment, or release treatment. There are no particular limitations on the thickness of the support film, but it is generally in the range of 10 to 150 ⁇ m, and preferably 25 to 50 ⁇ m.
  • the protective film is preferably made 1 to 40 ⁇ m thick.
  • the support film (Y) is peeled off after the resin composition layer (X) is laminated onto a circuit board, or after the resin composition layer (X) is heat-cured to form an insulating layer. If the support film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet is heat-cured, the adhesion of dust and the like during the curing process can be prevented. When the support film (Y) is peeled off after the resin composition layer (X) is heat-cured, the support film (Y) is previously subjected to a release treatment.
  • a multilayer printed circuit board can be manufactured from the resin sheet obtained as described above.
  • the protective film is peeled off from the resin composition layer (X), and then the resin composition layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method.
  • the lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and the circuit board may be heated (preheated) before lamination.
  • the lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140° C., a pressure bonding pressure of 1 to 11 kgf/cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N/m 2 ), and lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less air pressure.
  • the curable resin composition of the present invention can also be used to manufacture semiconductor devices.
  • semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (thin quad flat package), etc.
  • the curable resin composition of the present invention and its cured product can be used in a wide range of fields. Specifically, they can be used in various applications such as molding materials, adhesives, composite materials, and paints.
  • the cured product of the curable resin composition of the present invention exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), lightweight and high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.
  • GPC gel permeation chromatography
  • analysis equipment online degassing unit (DGU-20A), liquid delivery unit (LC-20AD), autosampler (SIL-20A), photodiode array detector (SPD-M40), column oven (CTO-20A), system controller (CBM-20A), all manufactured by Shimadzu Corporation
  • DGU-20A online degassing unit
  • LC-20AD liquid delivery unit
  • SIL-20A autosampler
  • SPD-M40 photodiode array detector
  • CTO-20A column oven
  • system controller CBM-20A
  • Example 1 A flask equipped with a thermometer, a cooling tube, and a stirrer was equipped with an aspirator and a base trap. To this flask, 20 parts of Tuftec M1913 (manufactured by Asahi Kasei Corporation) as an acid-modified hydrogenated thermoplastic styrene-based elastomer (AH-AB), 180 parts of toluene, and 0.34 parts of allylamine hydrochloride (manufactured by Tokyo Kasei Co., Ltd.) were added, and the mixture was reacted at 110°C for 12 hours while collecting the generated hydrogen chloride with a base trap.
  • Tuftec M1913 manufactured by Asahi Kasei Corporation
  • AH-AB acid-modified hydrogenated thermoplastic styrene-based elastomer
  • AH-AB acid-modified hydrogenated thermoplastic styrene-based elastomer
  • allylamine hydrochloride manufactured by Tokyo Kasei Co
  • Examples 2 and 3 Comparative Examples 1 and 2
  • polyphenylene ether compound SA-9000 (manufactured by SABIC), styrene butadiene rubber: Ricon-100 (manufactured by Cray Valley), and polymerization initiator: dicumyl peroxide (DCP) in the amounts shown in Table 1
  • a toluene solution with a solid content of 30% by weight was prepared in Examples 2 and 3
  • a toluene solution with a solid content of 70% by weight was prepared in Comparative Examples 1 and 2.
  • the toluene solution was applied to a mirror-finished copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) using an applicator with a coating thickness of 200 ⁇ m, and then cured in an inert oven at 220 ° C. for 2 hours to obtain a cured product.
  • a test piece of the desired size was cut out using a laser cutter as necessary.
  • SA-9000 Methacrylate-terminated polyphenylene ether (manufactured by SABIC) Ricon-100: Styrene butadiene rubber (manufactured by Cray Valley) ⁇ DCP: Dicumyl peroxide
  • the compounds of the present invention are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
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JPS63150304A (ja) * 1986-12-12 1988-06-23 Mitsubishi Petrochem Co Ltd 紫外線硬化性樹脂
US5026494A (en) * 1989-04-05 1991-06-25 Basf Amino group-containing graft polymer, and its use as a dispersing viscosity index improver
JPH03221513A (ja) * 1990-01-29 1991-09-30 Mitsubishi Petrochem Co Ltd グラフト共重合体の製造法

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JPS5819316A (ja) * 1981-07-27 1983-02-04 Denki Kagaku Kogyo Kk 熱硬化性樹脂
US4795692A (en) * 1987-02-02 1989-01-03 Eastman Kodak Company Negative-working polymers useful as X-ray or E-beam resists
JP7322877B2 (ja) * 2018-06-01 2023-08-08 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板
JP2023015005A (ja) * 2021-07-19 2023-01-31 日本化薬株式会社 硬化性樹脂組成物、プリプレグおよびその硬化物
JP2023015004A (ja) * 2021-07-19 2023-01-31 日本化薬株式会社 硬化性樹脂組成物、プリプレグおよびその硬化物
EP4335902A1 (en) * 2022-09-07 2024-03-13 Polyscope Polymers B.V. Low dielectric loss thermosetting resin composition

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JPS63150304A (ja) * 1986-12-12 1988-06-23 Mitsubishi Petrochem Co Ltd 紫外線硬化性樹脂
US5026494A (en) * 1989-04-05 1991-06-25 Basf Amino group-containing graft polymer, and its use as a dispersing viscosity index improver
JPH03221513A (ja) * 1990-01-29 1991-09-30 Mitsubishi Petrochem Co Ltd グラフト共重合体の製造法

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