Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
  • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
  • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
  • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
• • 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
  • C08F12/00—Homopolymers and 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
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • 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

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.
• CPUs central processing units
• the fifth-generation communication system is expected to further increase capacity and speed.
• 5G will use increasingly higher frequencies, but reducing transmission loss is crucial to achieving high-speed communication using high frequencies, requiring even lower dielectric properties from circuit board materials.
• Transmission loss on printed circuit boards is due to conductor loss and dielectric loss.
• conductor loss is proportional to the square root of the dielectric constant and dielectric loss tangent of the dielectric. Therefore, improving the dielectric loss tangent, which contributes more to transmission loss than the dielectric constant, is an effective way to reduce transmission loss.
• Low-dielectric materials include synthetic rubber materials such as SBR (styrene butadiene rubber) and polybutadiene, but these materials have issues such as low reactivity and high tackiness during prepreg creation. In light of this, there is a need for the development of thermosetting resins with excellent low dielectric properties.
• SBR styrene butadiene rubber
• Patent Document 1 proposes a composition containing maleimide resin and propenyl group-containing phenolic resin. However, since phenolic hydroxyl groups that are not involved in the curing reaction remain, the electrical properties are not sufficient.
• the present invention was made in light of these circumstances, and aims to provide a compound, a curable resin composition, and a cured product thereof that have excellent low dielectric properties.
• X represents a hydrocarbon group having 1 to 20 carbon atoms
• A represents a hydrocarbon group represented by the following formula (a) or formula (b).
• formulas (a) and (b) may be randomly bonded.
• m represents an integer of 0 to 20
• k represents an integer of 1 to 3
• the average value of m+k, (m+k) ave is 0 ⁇ (m+k) ave ⁇ 10.
• n represents the average number of repetitions, and 1 ⁇ n ⁇ 20.
• R1 represents a hydrocarbon group having 1 to 5 carbon atoms, and 1 is an integer of 0 to 2.
• X represents a hydrocarbon group having 1 to 20 carbon atoms
• A represents a hydrocarbon group represented by the following formula (a) or formula (b).
• formulas (a) and (b) may be randomly bonded.
• m represents an integer of 0 to 20
• k represents an integer of 1 to 3
• the average value of m+k, (m+k) ave is 0 ⁇ (m+k) ave ⁇ 10.
• n represents the average number of repetitions, and 1 ⁇ n ⁇ 20.
• R1 represents a hydrocarbon group having 1 to 5 carbon atoms
• 1 is an integer of 0 to 2
• Y represents a halogen atom.
• X represents a hydrocarbon group having 1 to 20 carbon atoms
• A represents a hydrocarbon group represented by the following formula (a) or formula (b).
• formulas (a) and (b) may be randomly bonded.
• m represents an integer of 0 to 20
• k represents an integer of 1 to 3
• the average value of m+k, (m+k) ave is 0 ⁇ (m+k) ave ⁇ 10.
• n represents the average number of repetitions, and 1 ⁇ n ⁇ 20.
• R1 represents a hydrocarbon group having 1 to 5 carbon atoms
• 1 is an integer of 0 to 2
• Y represents a halogen atom.
• * represents the benzene ring in formula (3) or the bonding position to the benzene ring in formulas (a) and (b).
• Multiple R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
• Multiple p's each independently represent an integer of 0 to 4.
• the present invention makes it possible to provide a compound and a curable resin composition with excellent low dielectric properties.
• 1 shows a GPC chart of Synthesis Example 1.
• the 1 H-NMR chart of Synthesis Example 1 is shown below.
• 1 shows a GPC chart of Synthesis Example 2.
• the 1 H-NMR chart of Synthesis Example 2 is shown below.
• 1 shows a GPC chart of Synthesis Example 3.
• the 1 H-NMR chart of Synthesis Example 3 is shown below.
• 1 shows a GPC chart of Synthesis Example 4.
• the 1 H-NMR chart of Synthesis Example 4 is shown below.
• X represents a hydrocarbon group having 1 to 20 carbon atoms
• A represents a hydrocarbon group represented by the following formula (a) or formula (b).
• m represents an integer of 0 to 10
• k represents an integer of 1 to 3
• the average value of m+k, (m+k) ave is 1 ⁇ (m+k) ave ⁇ 10.
• (m+k) ave may be calculated from the results of GPC analysis or NMR analysis. The values of the raw materials may also be taken into consideration.
• n is the average number of repeating units, and is 1 ⁇ n ⁇ 20, preferably 1.1 ⁇ n ⁇ 20, more preferably 1.1 ⁇ n ⁇ 10, and particularly preferably 1.1 ⁇ n ⁇ 5.
• R1 represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.
• Mw weight average molecular weight
• GPC gel permeation chromatography
• R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.
• the carbon number is 5 or less, molecular vibration is unlikely to occur when exposed to high frequency waves, resulting in excellent electrical properties.
• the R2 is a hydrogen atom, deterioration of the dielectric properties and water absorption properties associated with the generation of polar groups resulting from the oxidation reaction of the alkyl group during high-temperature storage tests can be suppressed.
• Multiple p's each independently represent an integer from 0 to 4, preferably 0.
• the weight average molecular weight of the compound represented by formula (1) above, as determined by gel permeation chromatography (GPC), is preferably 200 or more but less than 5,000, more preferably 300 or more but less than 3,000, and particularly preferably 400 or more but less than 2,000.
• the number average molecular weight is preferably 200 or more but less than 5,000, more preferably 250 or more but less than 2,000, and particularly preferably 300 or more but less than 1,000.
• a weight average molecular weight and number average molecular weight of less than 5,000 facilitates purification by washing with water, while a molecular weight of 200 or more prevents the target compound from volatilizing during the solvent distillation step.
• X is preferably one or more of (c) to (k) described in the following formula (2), and is particularly preferably (d) or (f).
• the compound represented by formula (1) above can be produced by any method, including dehydrohalogenation of a compound represented by formula (3) in a solvent in the presence of a basic catalyst.
• solvents include, but are not limited to, non-water-soluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone.
• non-water-soluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethy
• aprotic polar solvents can also be used in combination with the non-water-soluble solvents. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these solvents may be used in combination.
• an aprotic polar solvent it is preferable to use one with a higher boiling point than the non-water-soluble solvent used in combination.
• the catalyst is not particularly limited, but examples include basic catalysts such as sodium hydroxide, potassium hydroxide, and potassium carbonate.
• the dehydrohalogenation reaction of the compound represented by formula (1) may be carried out in an organic solvent in the presence of a base catalyst, and the resulting solution may be washed with water and then returned to the reaction vessel, where the base catalyst is added and the reaction is carried out again. This can increase the progress of the dehydrohalogenation reaction. In other words, it is possible to reduce the amount of residual halogen contained in the target compound.
• the amount of residual halogen is preferably 1 to 10,000 ppm, more preferably 1 to 1,000 ppm, and even more preferably 1 to 750 ppm. If the amount of residual halogen contained in the compound represented by formula (1) is high, molecular vibrations may occur when exposed to high frequency waves, adversely affecting electrical properties, particularly the dielectric loss tangent. Furthermore, if the residual halogen content is high, the risk of problems such as metal corrosion and ion migration increases in environmental tests such as HAST (High Accelerated Stress Test). Therefore, the above halogen content is preferable.
• the reaction temperature is preferably 0 to 120°C, more preferably 0 to 100°C, and even more preferably 0 to 80°C.
• the compound of this embodiment may undergo self-polymerization and gelation, resulting in a risk of gelation. At temperatures below the lower limit, the reaction may not proceed sufficiently.
• Post-reaction post-treatment may involve neutralization with an optional acid compound. If necessary, the reaction solution may be added with an alcohol compound, water, or the like to recover the target product as crystals. The resulting reaction solution or crystals may be redissolved in an optional solvent and subjected to an extraction step.
• aromatic hydrocarbon solvents such as toluene and xylene may be used alone, or non-aromatic hydrocarbons such as cyclohexane and methylcyclohexane may be used in combination.
• the organic layer is washed with water until the wastewater becomes neutral, and the target compound is obtained by distilling off the solvent using an evaporator or the like.
• Y represents a halogen atom, and from the viewpoints of reactivity and the stability of the raw materials, a bromine atom or a chlorine atom is preferred, with a bromine atom being particularly preferred.
• the definitions of X, A, and R1 , and the values of k, m, l, and n, and their preferred ranges, are the same as those in the above formula (1).
• R2s each independently represent a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.
• the carbon number is 5 or less, molecular vibration is unlikely to occur when exposed to high frequency waves, resulting in excellent electrical properties.
• the R2 is a hydrogen atom, deterioration of dielectric properties and water absorption properties associated with the generation of polar groups resulting from the oxidation reaction of alkyl groups during high-temperature storage tests can be suppressed.
• Multiple p's each independently represent an integer from 0 to 4, preferably 0.
• the molar ratio of formula (a) to formula (b) is preferably 1:2 to 1:5, more preferably 1:2 to 1:4.
• the method for producing the compound represented by formula (3) above is not particularly limited.
• Y is a bromo atom
• a compound having a 2-bromoethylbenzene structure may be self-polymerized in the presence of an acid catalyst such as hydrochloric acid or activated clay, and then reacted with a bis-halogenated methyl arene compound.
• a compound having a 2-bromoethylbenzene structure may be self-polymerized in the presence of an acid catalyst such as hydrochloric acid or activated clay, and then reacted with a bis-hydroxymethyl arene compound.
• a compound having a 2-bromoethylbenzene structure may be reacted with a bis-halogenated methyl arene compound in the presence of an acid catalyst such as hydrochloric acid or activated clay, and then the reaction product may be reacted with a compound having a 2-bromoethylbenzene structure.
• a compound having a 2-bromoethylbenzene structure may be reacted with a bis-hydroxymethyl arene compound in the presence of an acid catalyst such as hydrochloric acid or activated clay, and then the reaction product may be reacted with a compound having a 2-bromoethylbenzene structure.
• hydrochloric acid When hydrochloric acid is used as a catalyst, the product is neutralized with an alkali metal such as sodium hydroxide or potassium hydroxide, extracted with an aromatic hydrocarbon solvent such as toluene or xylene, washed with water until the wastewater becomes neutral, and the solvent is removed using an evaporator or similar device to obtain the desired compound having at least two 2-bromoethylbenzene structures in the molecule.
• an alkali metal such as sodium hydroxide or potassium hydroxide
• an aromatic hydrocarbon solvent such as toluene or xylene
• Compounds having a 2-bromoethylbenzene structure include, but are not limited to, 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, 1-(2-bromoethyl)-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethylbenzene, and 1-(2-bromoethyl)-2,6-dimethylbenzene.
• a larger carbon number improves solvent solubility but reduces heat resistance. Therefore, it is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, and most preferably unsubstituted or substituted with a methyl group.
• Examples of the bishalogenated methylaryl compounds include o-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, 4,4'-bisfluoromethylenebiphenyl, 4,4'-bischloromethylenebiphenyl, 4,4'-bisbromomethylenebiphenyl, 4,4'-bisio
• Examples of the halogen compound include 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bis
• chloride compounds, bromide compounds, and iodide compounds are preferred, and chloride compounds and bromide compounds are more preferred.
• Other optional halogen compounds include cyanurfluoride, cyanurchloride, cyanurbromide, and cyanuriodide, but are not limited thereto. isn't it.
• Bishydroxymethylaryl compounds include, but are not limited to, o-benzenedimethanol, m-benzenedimethanol, p-benzenedimethanol, 4,4'-bishydroxymethylbiphenyl, 2,4-bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,4-benzenedimethanol, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol, and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,2-benzenedimethanol. These compounds may be used alone or in combination.
• the amount used is preferably 0.01 to 0.8% by weight, more preferably 0.05 to 0.6% by weight, per 1% by weight of the compound having a 2-bromoethylbenzene structure.
• catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid can be used as needed.
• These include Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These may be used alone or in combination.
• the amount of catalyst used is preferably 0.1 to 50 wt %, and more preferably 1 to 40 wt %, based on the total weight of the compound represented by formula (3) used.
• reaction solution may become too viscous, making stirring difficult; if too little, the reaction may proceed slowly.
• the reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, or xylene, or may be carried out solvent-free.
• an acidic catalyst is added to a mixed solution of a compound having a 2-bromoethylbenzene structure, a bis(halogenated methylarylene) compound, and a solvent (or no solvent), and if the catalyst contains water, the water is removed from the system by azeotropy or other methods.
• the reaction is then carried out at 80 to 220°C, preferably 100 to 200°C, for 0.5 to 20 hours.
• the acidic catalyst may be neutralized with an alkaline aqueous solution, but it is also possible to proceed to the water washing step without neutralization.
• a water-insoluble organic solvent is added to the oil layer and water washing is repeated until the wastewater becomes neutral.
• the compound represented by formula (3) obtained by the above reaction may be continuously converted to the compound represented by formula (1) by adding an aromatic hydrocarbon solvent such as toluene or xylene, a non-aromatic hydrocarbon solvent such as cyclohexane or methylcyclohexane, or a neutralizing agent such as an alkali to the solution after the reaction, followed by the addition of an aprotic solvent and a base catalyst.
• an aromatic hydrocarbon solvent such as toluene or xylene
• a non-aromatic hydrocarbon solvent such as cyclohexane or methylcyclohexane
• a neutralizing agent such as an alkali
• the compound represented by formula (1) above can be cured by itself by heating or other means, but performance can also be improved by adding various materials to form a curable resin composition.
• the curability of the curable resin composition of the present embodiment can be improved 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, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being 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)phenol
• phosphines such as triphenylphosphine
• quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide. 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 can be a halogen, organic acid ion, hydroxide ion, or the like, but is not particularly specified; organic acid ions and hydroxide ions are particularly preferred), as well as transition metal compounds (transition metal salts) such as tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate esters (zinc octylphosphate, zinc stearylphosphate). These may be used alone or in combination.
• quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabuty
• the amount of 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 this embodiment 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, as well as inorganic fillers obtained by shaping these into a spherical or crushed form, but are not limited thereto. These may be used alone or in combination.
• the amount of inorganic filler used is 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. Furthermore, when obtaining a curable resin composition for use as an interlayer insulating layer forming material or a substrate material such as copper-clad laminates, prepregs, or RCC, the amount of inorganic filler used is 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 curability of the curable resin composition of this embodiment can be improved 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 thereof 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 that has curability and appropriate stability.
• the radical polymerization initiator is a compound that generates radicals upon irradiation with ultraviolet or visible light or heating, thereby initiating a chain polymerization reaction.
• Usable radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols.
• Organic peroxides are preferred because they are effective in controlling the curing temperature, suppress outgassing, and minimize the impact of decomposition products on electrical properties.
• 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-amylperoxy-2-ethylhexanoate, and t-butyl
• the peroxycarbonate include, but are not limited to, alkyl
• ketone peroxides diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, 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), and 2,2'-azobis(2,4-dimethylvaleronitrile). These compounds 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 part 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 polymerization inhibitor may be added during or after the synthesis of the compound of this embodiment.
• the amount of polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the compound of this embodiment.
• polymerization inhibitors examples include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors.
• One type of polymerization inhibitor may be used, or multiple types may be used in combination. Of these, in this embodiment, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors are preferred.
• phenolic 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-butylphenol),
• sulfur-based polymerization inhibitor 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 neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of suitable phosphites include t-buty
• Examples of the above hindered amine 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, and Tinuvin 791FB.
• 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 embodiment 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 retardants may be either reactive or additive.
• Specific examples include phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis(dixylylenyl phosphate), 1,4-phenylenebis(dixylylenyl phosphate), and 4,4'-biphenyl(dixylylenyl 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 resin with the active hydrogen of the above phosphanes;
• phosphate esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate), or phosphorus-containing epoxy compounds being particularly preferred.
• the content of 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, the flame retardancy may be insufficient, and if it is more than 0.6 part by mass, it may have a negative effect on the moisture absorption and dielectric properties of the cured product.
• the curable resin composition of this embodiment may contain a light stabilizer.
• a hindered amine-based light stabilizer particularly a HALS, is preferred as the light stabilizer.
• HALS include a reaction product 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, a reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and 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)buty
• Suitable hydroxybenzyl compounds include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These compounds may be used alone or in combination.
• 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. Less than 0.001 parts by mass may be insufficient to achieve light stabilization, while more than 0.1 parts by mass may have a negative impact on the moisture absorption and dielectric properties of the cured product.
• the curable resin composition of this embodiment may use a binder resin.
• binder resins include, but are not limited to, butyral-based resins, acetal-based resins, acrylic-based resins, epoxy-nylon-based resins, NBR-phenol-based resins, epoxy-NBR-based resins, and silicone-based 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 embodiment 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 additives added is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.
• the curable resin composition of this embodiment may further contain epoxy resins, active ester compounds, phenolic resins, polyphenylene ether compounds, amine resins, compounds having an ethylenically unsaturated bond, 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.
• polyphenylene ether compounds compounds having an ethylenically unsaturated bond, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof.
• the inclusion of these compounds can improve the brittleness of the cured product and adhesion to metals, and can suppress package cracking during reliability tests such as solder reflow and thermal cycling.
• the 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 this embodiment.
• the preferred lower limit is 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass.
• epoxy resin Preferred examples of epoxy resins include, but are not limited to, the following.
• 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 suitable 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-7200 manufactured by
• An active ester compound refers to a compound containing at least one ester bond in its structure, with an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond.
• Examples of active ester compounds include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. These compounds are obtained by a condensation reaction between at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound.
• active ester compounds are preferably obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. Active ester compounds may be used alone or in combination of two or more.
• carboxylic acid compound 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 examples include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and the phenolic resins described below.
• dicyclopentadiene-type diphenol compounds refer to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.
• 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 compound 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 “EXB9416-70BK” (manufactured by DIC Corporation) as a phenolic compound.
• 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 agents that are acetylated phenol novolac include “DC808” (manufactured by Mitsubishi Chemical Corporation), and phosphorus atom-containing active ester curing agents include "EXB-9050L-62M” (manufactured by DIC Corporation).
• 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. If the ratio is outside this range, excess epoxy groups or active ester groups may remain in the system, which may result in deterioration of properties in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature, high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).
• a phenolic resin is a compound having two or more phenolic hydroxyl groups in the molecule.
• phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these.
• Phenol alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, 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 compounds 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 Corporation, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, Inc., a polyphenylene ether compound having a styrene structure).
• the number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5,000, more preferably 2,000 to 5,000, and even more preferably 2,000 to 4,000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. On the other hand, if the molecular weight is greater than 5,000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to result in 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 tends to lower the glass transition temperature of the cured product and reduce 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 or the like.
• the polyphenylene ether compound may be obtained by a polymerization reaction or by a redistribution reaction of a high-molecular-weight polyphenylene ether compound with a number-average molecular weight of approximately 10,000 to 30,000. These compounds may also be used as raw materials and imparted with radical polymerization properties by reacting them with a compound having an ethylenically unsaturated bond, such as methacrylic acid chloride, acrylic acid chloride, or chloromethylstyrene.
• a polyphenylene ether compound obtained by a 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.
• Polyphenylene ether compounds obtained by such a redistribution reaction are preferred because they maintain even higher heat resistance due to the presence of hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain.
• functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond.
• polyphenylene ether compounds obtained by a polymerization reaction are preferred because they exhibit excellent fluidity.
• the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc.
• the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions, etc. of the redistribution reaction. More specifically, one possible approach is to adjust the amount of phenolic compound used in the redistribution reaction. In other words, the greater the amount of phenolic compound used, the lower the molecular weight of the resulting 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 preferred are, for example, multifunctional phenolic compounds having two or more phenolic hydroxyl groups per molecule, such as bisphenol A, phenol novolac, and cresol novolac. These compounds may be used alone or in combination.
• the content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1,000 parts by mass, and more preferably 10 to 750 parts by mass, per 100 parts by mass of the curable resin composition.
• a polyphenylene ether compound content within the above range is preferable in that it not only has excellent heat resistance, but also allows for a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.
• An 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 the reaction of aniline and xylylene chloride.
• aniline resins include, but are not limited to, aniline resins disclosed in Japanese Patent No. 6,429,862, reaction products of aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), reaction products of aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, reaction products of aniline and diisopropenylbenzene, and dimer diamine. 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 compounds containing an ethylenically unsaturated bond include, but are not limited to, reaction products of the above-mentioned phenolic resins with ethylenically unsaturated bond-containing halogen-based compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated bond-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of
• 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-xylene diisocyanate, m-xylene 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 biuret compounds
• 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 polymerization products of lactam compounds. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these.
• ⁇ Diisocyanate> benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like.
• ⁇ 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, 4,4'-dicarboxydiphenyl sulfide, and the like.
• ⁇ 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, dodecanediol 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 above diamines with the following tetracarboxylic dianhydrides. These may be used alone or in combination.
• the curable resin composition of this embodiment may contain a maleimide compound.
• a maleimide compound is a compound having one or more maleimide groups in the molecule.
• maleimide compounds 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 Xyloc-type maleimide compounds (anilix).
• maleimide manufactured by Mitsui Chemicals Fine Co., Ltd.
• biphenylaralkyl-type maleimide compounds 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 compounds 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 - Curing Agent CAS Number Memorandum No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No.
• Suitable 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)" published in February 2019. These compounds may be used alone or in combination.
• the cyanate ester resin is a cyanate ester compound obtained by reacting a phenolic resin with a cyanogen halide.
• a cyanogen halide include, but are not limited to, 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
• the cyanate ester compound is particularly preferred as the cyanate ester compound because it has low moisture absorption, 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 and form a sym-triazine ring.
• the catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and 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 polybutadienes include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. 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, and RICON-184 (all manufactured by Cray Valley Chemical Industries, Ltd.) and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.).
• polybutadienes examples include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.).
• the molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight-average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000.
• the amount of volatilization is high, making it difficult to adjust the solids content during prepreg production.
• compatibility with other curable resins deteriorates.
• compounds containing heteroatoms such as oxygen and nitrogen such as bismaleimides and polymaleimides, have difficulty ensuring compatibility with low-polarity compounds, such as compounds composed primarily of hydrocarbons or compounds composed solely of hydrocarbons, due to their polarity.
• the compound of this embodiment does not have a skeleton design that actively incorporates heteroatoms such as oxygen and nitrogen, and therefore exhibits excellent compatibility with materials with low polarity and low dielectric properties, as well as compounds composed solely of hydrocarbons.
• 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,
• Suitable block copolymers include SEPTON 8004, SEPTON 8006, and SEPTON 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a styrene-ethylene/ethylene propylene-styrene block copolymer having a hydroxyl group at its terminal: SEPTON HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: SEPTON 5125 and SEPTON 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: HYBRAR 7125F and HYBRAR 7311F, both manufactured by Kuraray Co., Ltd.), and SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T
• Polystyrene and modified products thereof are preferably free of unsaturated bonds because they have higher heat resistance and are less susceptible to oxidative degradation.
• the weight-average molecular weight of polystyrene 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 polyphenylene ether compounds, 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. Therefore, a weight-average molecular weight of about 10,000 to 300,000 is preferred.
• Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule.
• Examples of polyethylene and modified polyethylenes 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, and ethylene-vinyl acetate copolymers, but are not limited thereto.
• ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure may be used alone or in combination.
• weight-average molecular weight of polyethylene and modified polyethylenes thereof there are no particular restrictions on the weight-average molecular weight of polyethylene and modified polyethylenes thereof as long as it is 10,000 or more.
• 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.
• any compound may be used as long as it is a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group.
• the compound having a phenolic hydroxyl group is not particularly limited, but for example, the above-mentioned phenolic resin, phenols (which may have a substituent such as an alkenyl group or an alkyl group), and bisphenols can be used.
• the compound having an amino group is not particularly limited, but the above-mentioned amine resin, diamine, and anilines (which may have a substituent such as an alkenyl group or an alkyl group) can be used.
• the aldehyde compound for example, the above-mentioned aldehydes can be used, but formaldehyde is preferably used.
• benzoxazine compounds may be used, and examples thereof include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).
• the curable resin composition of this embodiment can be obtained by preparing the above components in a predetermined ratio, pre-curing the composition at 130 to 180°C for 30 to 500 seconds, and then post-curing the composition at 150 to 200°C for 2 to 15 hours, thereby allowing the curing reaction to proceed sufficiently and producing a cured product of this embodiment.
• the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed before curing.
• the method for preparing the curable resin composition of this embodiment is not particularly limited, but the components may be simply mixed uniformly, or they may be prepolymerized.
• a mixture containing the compound of this embodiment is prepolymerized by heating it in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent.
• compounds such as 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 and prepolymerized.
• the components may be mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or a reaction vessel equipped with a stirrer in the presence of a solvent.
• the uniform mixing method involves kneading the components using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform resin composition.
• the resulting resin composition is then pulverized and molded into cylindrical tablets using a molding machine such as a tablet machine, or into a granular powder or powder molded body.
• these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition.
• the resulting molded body is non-sticky at 0 to 20°C, and there is little decrease in fluidity or curability even when stored at -25 to 0°C for one week or more.
• the resulting molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.
• the curable resin composition of this embodiment can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent.
• the curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone, as needed, to form a varnish.
• This varnish can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg.
• This prepreg can then be hot-press molded to form a cured product of the curable resin composition of this embodiment.
• the solvent used in this case accounts for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of this embodiment and the solvent.
• a curable resin composition containing carbon fiber can be obtained directly, for example, by the RTM method.
• the curable resin composition of this embodiment 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 this embodiment as a varnish onto a release film, removing the solvent under heat, and then performing B-stage formation.
• This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.
• the curable resin composition of this embodiment can also be used to obtain a prepreg by heating and melting it to reduce its viscosity and impregnating it into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
• reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
• specific examples include, but are not limited to, 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; inorganic fibers other than glass; and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fiber.
• Kevlar registered trademark
• the shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat.
• woven fabrics include plain weave, sieve weave, and twill weave, and these can be selected appropriately from these known methods depending on the intended application 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.
• the thickness of the substrate is not particularly limited, but is preferably approximately 0.01 to 0.4 mm. Prepreg can also be obtained by impregnating reinforcing fibers with the varnish and then drying them by heating.
• a laminate can also be manufactured using the prepreg.
• the laminate is not particularly limited as long as it comprises one or more prepregs, and may also have any other layers.
• the method for manufacturing the laminate can be any generally known method, and is not particularly limited. For example, when molding a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used.
• the prepregs are laminated together and then heated and pressure molded to obtain a laminate.
• the heating temperature is not particularly limited, but is preferably 65 to 300°C, and more preferably 120 to 270°C.
• the pressure applied is also not particularly limited, but if the pressure is too high, it becomes difficult to adjust the solid content of the resin in the laminate, resulting in unstable quality. If the pressure is too low, air bubbles will form and adhesion between the laminate layers will be poor. Therefore, a pressure of 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred.
• the laminate of this embodiment, having a layer made of metal foil can be suitably used as a metal foil-clad laminate, as described below.
• the prepreg is cut into a desired shape and laminated with copper foil or the like as needed.
• the laminate is then heated and cured while applying pressure to the laminate 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 this embodiment can also be made into a resin sheet.
• One method for obtaining a resin sheet from the curable resin composition of this embodiment is to apply the curable resin composition to a support film (support), followed by drying to form a resin composition layer on the support film.
• the film softens under the lamination temperature conditions (70°C to 140°C) used in vacuum lamination and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components to achieve this characteristic.
• the resulting resin sheet or circuit board (such as a copper-clad laminate) must have a uniform appearance to ensure consistent performance at any given location without experiencing locally varying property values due to phase separation or other factors.
• the diameter of the through holes in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, and it is preferable to be able to fill them with resin within this range. Furthermore, if both sides of the circuit board are laminated, it is desirable to fill about half of the through holes.
• a specific method for producing the above-mentioned resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying 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 way that the nonvolatile content is 30 to 60% by mass of the total.
• the thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer of the circuit board onto 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 this embodiment may be protected with a protective film, which will be described later. Protection with a protective film can prevent the adhesion of dust and other particles to the surface of the resin composition layer (X) and scratches.
• the support film and protective film can 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 restrictions on the thickness of the support film, but it is generally between 10 and 150 ⁇ m, and preferably between 25 and 50 ⁇ m.
• the thickness of the protective film is preferably between 1 and 40 ⁇ m.
• the support film (Y) is peeled off after the resin composition layer (X) has been laminated onto the circuit board, or after the resin composition layer (X) has been heat-cured to form an insulating layer. Peeling off the support film (Y) after the resin composition layer (X) that constitutes the resin sheet has been heat-cured can prevent the adhesion of dust and other particles during the curing process. If the support film (Y) is to be peeled off after the resin composition layer (X) has been cured, a release treatment is applied to the support film (Y) beforehand.
• a multilayer printed circuit board can be produced from the resin sheet obtained as described above.
• the protective film is peeled off, and then the resin composition layer (X) is laminated to 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 circuit board may be heated (preheated) before lamination.
• a pressure bonding temperature (lamination temperature) of 70 to 140°C is preferred, a pressure bonding pressure of 1 to 11 kgf/cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N/m 2 ) is preferred, and lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less.
• the curable resin composition of this embodiment can 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), and TQFP (thin quad flat package).
• the curable resin composition and its cured product of this embodiment can be used in a wide range of fields. Specifically, they can be used in a variety of applications, including molding materials, adhesives, composite materials, and paints. Because the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is 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, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.
• 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, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing
• A represents a hydrocarbon group represented by the following formula (b-2) or (b-3):
• * represents the bonding position to the benzene ring in formula (b-1) or the benzene ring in formulas (b-2) and (b-3).
• the ratio of (b-5) to (b-6) in A in the following formula (b-4) calculated from these was 1:3.2. Furthermore, a signal for terminal hydrogen of the vinyl group derived from the following formula (b-4) was observed at 5.00-6.00 ppm, and a signal for methylene bridge hydrogen was observed at 3.60-4.10 ppm. The integral value of the peak derived from the terminal hydrogen of the vinyl group was 7.9, and the integral value of the peak derived from the hydrogen of the methylene bridge was 9.1. The value of n in the following formula (b-4) calculated from these was 1.2.
• A represents a hydrocarbon group represented by the following formula (b-5) or (b-6):
• * represents the bonding position to the benzene ring of formula (b-4) or the benzene ring of formulas (b-5) and (b-6).
• A represents a hydrocarbon group represented by the following formula (b-8) or (b-9):
• * represents the bonding position to the benzene ring in formula (b-7) or the benzene ring in formulas (b-8) and (b-9).
• the ratio of (b-11) to (b-12) in A of the following formula (b-10) calculated from these values was 1:1.4. Furthermore, a signal for terminal hydrogen of the vinyl group derived from the following formula (b-10) was observed at 5.00-6.80 ppm, and a signal for methylene bridge hydrogen was observed at 3.80-4.10 ppm. The integral value of the peak derived from terminal hydrogen of the vinyl group was 1.9, and the integral value of the peak derived from hydrogen of the methylene bridge was 3.0. The value of n in the following formula (b-10) calculated from this was 1.6.
• A represents a hydrocarbon group represented by the following formula (b-11) or (b-12):
• * represents the bonding position to the benzene ring of formula (b-10) or the benzene ring of formulas (b-11) and (b-12).
• ⁇ Dielectric tangent test> The test was performed at 25°C using a 10 GHz cavity resonator manufactured by AET Co., Ltd., using a cavity resonator perturbation method. The test was performed on a sample with a width of 1.7 mm, a length of 100 mm, and a thickness of 0.3 mm. The evaluation results are shown in Table 1.
• the compound of the present invention is suitably used in electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

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