WO2022186030A1 - 化合物、混合物、硬化性樹脂組成物およびその硬化物 - Google Patents

化合物、混合物、硬化性樹脂組成物およびその硬化物 Download PDF

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WO2022186030A1
WO2022186030A1 PCT/JP2022/007527 JP2022007527W WO2022186030A1 WO 2022186030 A1 WO2022186030 A1 WO 2022186030A1 JP 2022007527 W JP2022007527 W JP 2022007527W WO 2022186030 A1 WO2022186030 A1 WO 2022186030A1
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formula
compound
group
curable resin
resin composition
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French (fr)
Japanese (ja)
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隆行 遠島
政隆 中西
昌典 橋本
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2022541781A priority Critical patent/JP7241246B2/ja
Priority to KR1020237029210A priority patent/KR102844304B1/ko
Priority to CN202280018318.5A priority patent/CN116917258A/zh
Publication of WO2022186030A1 publication Critical patent/WO2022186030A1/ja
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/285—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/16—End groups
    • C08G2261/164—End groups comprising organic end groups
    • C08G2261/1642—End groups comprising organic end groups comprising reactive double bonds or triple bonds
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain

Definitions

  • the present invention relates to compounds, mixtures, curable resin compositions, and cured products thereof, and includes electrical and electronic components such as semiconductor sealing materials, printed wiring boards, and build-up laminates, carbon fiber reinforced plastics, and glass fibers. Lightweight high-strength materials such as reinforced plastics are well suited for 3D printing applications.
  • CPUs central processing units
  • PKG semiconductor packages
  • PCB motherboard
  • Non-Patent Document 1 Conductor loss is caused by the resistance component of conductors such as wiring on a substrate, and is divided into loss due to the skin effect at high frequencies and scattering loss due to the roughness of the copper foil surface.
  • SiC semiconductors have begun to be used in trains, air conditioners, and the like, and the encapsulating material for semiconductor elements is required to have extremely high heat resistance.
  • Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin.
  • Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are substituted with allyl groups.
  • Claisen rearrangement occurs at 190°C, and at 200°C, which is a general substrate molding temperature, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so electrical properties cannot be satisfied. do not have.
  • the present invention has been made in view of such circumstances, and provides compounds, mixtures, curable resin compositions, and cured products thereof exhibiting excellent heat resistance, electrical properties, adhesion, and good curability. intended to provide
  • X represents an arbitrary organic group.
  • the multiple Xs may be the same or different.
  • A is a methylene group or an oxygen atom
  • Q represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.
  • a plurality of R may be the same or different
  • R is a hydrocarbon group having 1 to 10 carbon atoms, or represents a halogenated alkyl group.
  • the multiple Rs may be the same or different.l and m each represent an integer of 0 to 3, and n is a repeating unit.
  • s is a repeating unit, and 1 ⁇ s ⁇ 20.
  • a curable resin composition containing the compound according to any one of [1] to [4] above or the mixture according to [5] above.
  • the curable resin composition according to [6] above further containing one or more selected from the group consisting of polyphenylene ether, polybutadiene and modified products thereof.
  • the curable resin composition according to [7] above, wherein the polybutadiene and its modified product contain one or more selected from the group consisting of a styrene-butadiene copolymer and a butadiene-based thermoplastic elastomer.
  • X represents an arbitrary organic group.
  • the multiple Xs may be the same or different.
  • Z represents a halogen element. Multiple Z may be the same or different, A is a methylene group or an oxygen atom, Q is a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group, and multiple Rs are may be the same or different.
  • R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.When there are multiple Rs, the multiple Rs may be the same l and m each represent an integer of 0 to 3, n is a repeating unit and satisfies 1 ⁇ n ⁇ 20, p is a repeating unit and satisfies 1 ⁇ p ⁇ 20.
  • the compound of the present invention has excellent curability, and its cured product has high heat resistance, low dielectric properties, and excellent adhesion. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, and the like. In addition, since the compound of the present invention is excellent in reactivity, curing alone is also one of preferred embodiments.
  • FIG. 1 shows a GPC chart of Example 1.
  • FIG. 1 H-NMR chart of Example 1 is shown.
  • 2 shows a GPC chart of Example 2.
  • FIG. 1 H-NMR chart of Example 2 is shown.
  • the GPC chart of Example 3 is shown.
  • 1 H-NMR chart of Example 3 is shown.
  • the GPC chart of Example 4 is shown.
  • a GPC chart of Reference Example 1 is shown.
  • 1 H-NMR chart of Reference Example 1 is shown.
  • a GPC chart of Reference Example 2 is shown. 1 H-NMR chart of Reference Example 2 is shown.
  • the compound of the present invention is represented by the following formula (1).
  • X represents an arbitrary organic group.
  • the multiple Xs may be the same or different.
  • A is a methylene group or an oxygen atom
  • Q represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.
  • a plurality of R may be the same or different
  • R is a hydrocarbon group having 1 to 10 carbon atoms, or represents a halogenated alkyl group.
  • the multiple Rs may be the same or different.
  • l and m each represent an integer of 0 to 3, and n is a repeating unit. , 1 ⁇ n ⁇ 20, p is a repeating unit, and 1 ⁇ p ⁇ 20.
  • n is usually 1 ⁇ n ⁇ 20, preferably 1.1 ⁇ n ⁇ 20, more preferably 1.1 ⁇ n ⁇ 10, particularly 1.1 ⁇ n ⁇ 5 preferable.
  • Mw weight average molecular weight of the olefin compound determined by gel permeation chromatography
  • the weight average molecular weight is preferably 200 or more and less than 5,000, more preferably 300 or more and less than 3,000, and particularly preferably 400 or more and less than 2,000.
  • p is usually 1 ⁇ p ⁇ 20, preferably 1 ⁇ p ⁇ 5, more preferably 1 ⁇ p ⁇ 3, and particularly preferably 1 ⁇ p ⁇ 2.
  • R is usually a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Hydrocarbons in which R has 3 or less carbon atoms are less susceptible to molecular vibration when exposed to high frequency waves, and are therefore excellent in electrical properties.
  • Q is generally a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Hydrocarbons with 3 or less carbon atoms are less susceptible to molecular vibration when exposed to high frequency waves, and are therefore excellent in electrical properties.
  • l is usually 0 to 3, preferably 0 to 2, more preferably 0. When l is 0, it can be said that it is particularly preferable from the viewpoint of molecular symmetry. When it has a highly symmetrical molecular structure, it is easy to obtain a cured product with a highly symmetrical chemical bond pattern.
  • a cured product with a highly symmetrical chemical bond mode is less likely to undergo molecular vibration and has the effect of canceling out dipoles, resulting in excellent dielectric properties. Also, introducing a compound having two or more aromatic rings in the molecule such as diphenylmethane into the molecule lowers the functional group density, thereby exhibiting the effect of reducing cure shrinkage. The smaller the curing shrinkage, the easier it is to improve the adhesion to copper foil and the like.
  • X is preferably any one or more of (a) to (h) described in the following formula (2), and (a) to (c) and (e) to (h) is more preferred, and (a) is particularly preferred. This is because as the conjugation of the aromatic ring increases, the dipole moment increases, possibly deteriorating the dielectric properties.
  • the compound represented by the formula (1) of the present invention is derived from the compound represented by the following formula (3).
  • X represents an arbitrary organic group.
  • the multiple Xs may be the same or different.
  • Z represents a halogen element. Multiple Z may be the same or different, A is a methylene group or an oxygen atom, Q is a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated alkyl group, and multiple Rs are may be the same or different.
  • R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.When there are multiple Rs, the multiple Rs may be the same l and m each represent an integer of 0 to 3, n is a repeating unit and satisfies 1 ⁇ n ⁇ 20, p is a repeating unit and satisfies 1 ⁇ p ⁇ 20. be.
  • Z is preferably a bromine atom or a chlorine atom, and particularly preferably a bromine atom.
  • the compound represented by the formula (1) of the present invention is derived from the compound represented by the formula (3). Specifically, it can be obtained by subjecting the compound represented by the formula (3) to a dehydrohalogenation reaction in a solvent in the presence of a basic catalyst. Further, in order to improve the reaction rate of the dehydrohalogenation reaction, the solution subjected to the dehydrohalogenation reaction is washed with water to remove salts, returned to the reaction vessel, and subjected to the dehydrohalogenation reaction again. You can do it multiple times.
  • the amount of halogen remaining in the obtained olefin resin is preferably 10 to 10,000 ppm, more preferably 10 to 1,000 ppm, and more preferably 10 to 900 ppm.
  • solvents to be used include 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 methyl isobutyl.
  • Water-insoluble solvents such as ketone-based solvents such as ketones, cyclopentanone, and acetone can be used, but the solvents are not limited to these, and two or more of them may be used in combination.
  • An aprotic polar solvent can also be used in combination with the water-insoluble solvent.
  • examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more of them may be used in combination.
  • the catalyst is not particularly limited, basic catalysts such as sodium hydroxide, potassium hydroxide and potassium carbonate can be used.
  • the method for producing the compound represented by the formula (3) is not particularly limited.
  • the reaction may be carried out under an acid catalyst such as an acid or activated clay, or a compound having a 2-bromoethylbenzene structure, a bishydroxymethylaryl compound and a diphenylmethane compound or a diphenyl ether compound may be reacted with an acid such as hydrochloric acid, sulfonic acid, or activated clay.
  • the reaction may be carried out under a catalyst.
  • hydrochloric acid neutralize with an alkali metal such as sodium hydroxide or potassium hydroxide, extract with an aromatic hydrocarbon solvent such as toluene or xylene, wash with water until the waste water becomes neutral, and evaporate.
  • the charging ratio of the bishalogenated methylaryl compound (or bishydroxymethylaryl compound) to 1 mol of the compound having a 2-bromoethylbenzene structure is preferably 0.1 to 0.95 mol, more preferably 0.2 to 0.9 mol. Preferably, 0.25 to 0.8 mol is particularly preferred.
  • the ratio of the diphenylmethane compound or diphenyl ether compound to 1 mol of the bishalogenated methylaryl compound (or bishydroxymethylaryl compound) is preferably 0.1 to 0.95 mol, more preferably 0.2 to 0.2 mol. 9 mol is more preferred, and 0.25 to 0.8 mol is particularly preferred.
  • the effect of introducing a diphenylmethane structure or a diphenyl ether structure can be exhibited without residual raw materials.
  • Compounds having a 2-bromoethylbenzene structure include 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, Examples include, but are not limited to, 1-(2-bromoethyl)-2,6-dimethylbenzene. If the number of carbon atoms is large, the solvent solubility is improved, but the heat resistance is lowered. more preferably substituted with a group, and most preferably unsubstituted or substituted with a methyl group.
  • Bishalogenated methylaryl compounds include eaux-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, Occasionally-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, Occasionally- 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'-bisiodomethylenebiphenyl, 2,4-bisfluoromethylenebiphenyl, 2,4-bischloromethylenebiphenyl, 2,4-bis Bromo
  • the bishydroxymethylaryl compounds include o-benzenedimethanol, m-benzenedimethanol, p-benzenedimethanol, 4,4'-bishydroxymethylbiphenyl, 2,4-bishydroxymethylbiphenyl, 2,2'- Bishydroxymethylbiphenyl, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,4-benzenedimethanol, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethyl-1,2-benzenedimethanol and the like, but are not limited thereto. These may be used alone or in combination of two or more.
  • hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, as well as aluminum chloride and zinc chloride are used as catalysts.
  • Lewis acid, activated clay, acid clay, white carbon, zeolite, solid acid such as silica alumina, acidic ion exchange resin, and the like can be used. These may be used alone or in combination of two or more.
  • the amount of the catalyst to be used is generally 0.1-0.8 mol, preferably 0.2-0.7 mol, per 1 mol of the compound having a 2-bromoethylbenzene structure. If the amount of the catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult.
  • the reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, xylene, etc., optionally selected, or may be carried out without a solvent.
  • the water is azeotropically removed from the system. After that, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C for 0.5 to 20 hours.
  • the acidic catalyst is neutralized with an alkaline aqueous solution, and a non-water-soluble organic solvent is added to the oil layer, and washing with water is repeated until the wastewater becomes neutral.
  • the softening point of the compound represented by the formula (3) is preferably 80°C or lower, more preferably 70°C or lower.
  • the softening point is 80° C. or less, the viscosity of the olefin resin becomes low, and the impregnation of carbon fibers and glass fibers becomes easy. If the dilution solvent is increased to lower the viscosity, the resin may not sufficiently adhere to the fibrous material in the impregnation step.
  • the mixture of the present invention contains the compound represented by the above formula (1) and the compound represented by the following formula (4).
  • the mixture of the present invention particularly preferably contains a compound represented by the following formula (4-a).
  • the compound represented by the formula (1) is derived from the compound represented by the formula (3). If the isolation step is not included, the compound represented by the above formula (3) is produced containing a certain amount of the compound represented by the following formula (5).
  • the content ratio of the compound represented by the formula (1) and the compound represented by the formula (4) can be defined using GPC (detector: RI), and the formula It is calculated from the mononuclear peak ratios of the compounds represented by (1) and (4).
  • the mononuclear compound of the compound represented by the formula (1) is a component in which p and n in the formula (1) are 1, and the mononuclear compound of the compound represented by the formula (4) is It is a component in which p and s in the formula (4) are 1.
  • ⁇ / ⁇ is 0.1 to 2. 0.0, more preferably 0.2 to 1.5, even more preferably 0.3 to 1.0. Within this range, the mixture of the present invention can improve adhesion without significantly impairing heat resistance.
  • a composition containing the compound or mixture of the present invention contains a polymerization inhibitor.
  • Polymerization inhibitors that can be used include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based polymerization inhibitors.
  • the polymerization inhibitor may be added when synthesizing the compound represented by formula (1), or after synthesis.
  • a polymerization inhibitor can be used individually or in combination of 2 or more types.
  • the amount of polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component.
  • Each of these polymerization inhibitors can be used alone, but two or more of them may be used in combination.
  • phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based solvents are preferred.
  • the nitroxyl radical type is particularly preferable because of its excellent storage stability.
  • phenolic polymerization inhibitors include 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) -monophenols such as 6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol;2 , 2′-methylenebis(4-methyl-6-t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-t
  • sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like. be done.
  • phosphorus-based polymerization inhibitors include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, diisodecylpentaerythritolphosphite, tris(2,4-di-t -butylphenyl)phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbi(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbi(2, Phosphites such as 4-di-t-butyl-4-methylphenyl)phosphite and bis[2-t-butyl-6-methyl-4- ⁇ 2-(oct)
  • hindered amine-based polymerization inhibitors include Adekastave LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, and Adekastab LA.
  • nitroso-based polymerization inhibitor examples include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, (cupferron), and the like, preferably ammonium of N-nitrosophenylhydroxyamine. It is salt (cupferon).
  • nitroxyl radical polymerization inhibitors include 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, 4-benzoyloxy-2,2,6,6 -tetramethylpiperidine-1-oxyl and the like, but are not limited to these.
  • the curable resin composition of the present invention can use any known material as a curable resin other than the compound or mixture of the present invention.
  • Specific examples include phenol resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, propenyl resins, methallyl resins, active ester resins, and the like. may be used in combination.
  • the amount of the curable resin used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less the compound represented by the formula (1).
  • the lower limit is preferably 0.5 times by mass or more, more preferably 1 time by mass or more. If the amount is 10 times by mass or less, the effect of the heat resistance and dielectric properties of the compound represented by the formula (1) can be utilized.
  • phenol resins epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins
  • epoxy resins epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins
  • Phenolic resin phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyln
  • Epoxy resins glycidyl ether-based epoxy resins obtained by glycidylating the above phenolic resins, alcohols, etc., 4-vinyl-1-cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexane carboxylate, etc. Alicyclic epoxy resins, glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins.
  • TGDDM tetraglycidyldiaminodiphenylmethane
  • Amine resins diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolak, orthoethylaniline novolak, aniline resin obtained by reaction of aniline with xylylene chloride, aniline described in Japanese Patent No.
  • Active alkene-containing resins Polycondensates of the above phenol resins and active alkene-containing halogen compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), active alkene-containing phenols (2- allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4 -Bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.) polycondensates, epoxy resins or alcohols and substituted or non-substituted Polycondensates of substituted acrylates (acrylates,
  • Isocyanate resins p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, etc.
  • Aromatic diisocyanates areophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate and other aliphatic or alicyclic diisocyanates; one or more types of isocyanate monomers or an isocyanate trimerized from the above diisocyanate compound; a polyisocyanate obtained by a urethanization reaction between the above isocyanate compound and a polyol compound.
  • Polyamide resins amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.), lactams ( ⁇ -caprolactam, ⁇ -undecanelactam, ⁇ -laurolactam) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, Aliphatic diamines such as heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopent
  • Polyimide resin the above diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl- Cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetra Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'
  • Cyanate ester resin A cyanate ester compound obtained by reacting a phenolic resin with cyanogen halide.
  • Specific examples 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 novolak cyanate, and phenol/dicyclopentadiene cocondensate
  • cyanate ester compounds whose synthesis method is described in JP-A-2005-264154 are particularly preferable as cyanate ester compounds because they are excellent in low hygroscopicity, flame retardancy and dielectric properties.
  • the cyanate ester resin may be zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, Catalysts such as lead acetylacetonate, dibutyltin maleate, and the like can also be included.
  • the catalyst is usually used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the total weight of the curable resin composition.
  • Active ester resin A compound having one or more active ester groups in one molecule, such as an epoxy resin, is optionally used as a curing agent for a curable resin other than the compound represented by the formula (1) of the present invention. be able to.
  • Active ester curing agents 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. preferable.
  • the active ester curing agent is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and a thiol compound.
  • an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound. agents are preferred.
  • carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like.
  • dicyclopentadiene-type diphenol compound refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
  • the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and a benzoylated phenol novolac.
  • “Dicyclopentadiene-type diphenol structure” represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
  • Active ester curing agents include, for example, active ester compounds containing a dicyclopentadiene type diphenol structure such as "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC- 8000H-65TM”, “EXB-8000L-65TM”, “EXB-8150-65T” (manufactured by DIC); “EXB9416-70BK” (manufactured by DIC) as an active ester compound containing a naphthalene structure; acetylated phenol novolac "DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing "DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent; "EXB-90
  • the curable resin composition of the present invention can also be used in combination with a curing accelerator (curing catalyst) to improve curability.
  • a curing accelerator curing catalyst
  • Radical polymerization initiators that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, 1,3-bis-(t-butylperoxy Isopropyl)-benzene and other dialkyl peroxides, t-butyl peroxybenzoate, 1,1-di-t-butylperoxycyclohexane and other peroxyketals, ⁇ -cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butyl peroxy-2-ethylhexanoate, t
  • the amount of the radical polymerization initiator to be added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is too large, the molecular weight will not be sufficiently elongated during the polymerization reaction.
  • a curing accelerator other than the radical polymerization initiator may be added or used together.
  • curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo ( 5,4,0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, quaternary phosphonium salts such as tetrabutylphosphon
  • tin octylate zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behene transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid, zinc mystate) and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate, etc.);
  • a blending amount of the curing accelerator is 0.01 to 5.0 parts by weight based on 100 parts of the epoxy resin.
  • the curable resin composition of the present invention can also contain a phosphorus-containing compound as a component for imparting flame retardancy.
  • the phosphorus-containing compound may be of a reactive type or an additive type.
  • Specific examples of phosphorus-containing compounds include 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), 4,4'-biphenyl (dixylylenyl phosphate) and other phosphoric acid esters; 9,10-dihydro-9-oxa -phosphanes such as 10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-o
  • (phosphorus-containing compound)/(total epoxy resin) is preferably in the range of 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardance is insufficient, and if it is more than 0.6, there is a concern that the hygroscopicity and dielectric properties of the cured product may be adversely affected.
  • a light stabilizer may be added to the curable resin composition of the present invention, if necessary.
  • Hindered amine-based light stabilizers particularly HALS, are suitable as the light stabilizer.
  • HALS are not particularly limited, but representative ones include dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4- Polycondensation product of piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, 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-
  • the curable resin composition of the present invention can be blended with a binder resin as needed.
  • binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. , but not limited to these.
  • the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, preferably 0.05 to 50 parts by mass, more preferably 0.05 to 50 parts by mass based on 100 parts by mass of the resin component. 0.05 to 20 parts by weight are used as needed.
  • the curable resin composition of the present invention may optionally contain fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia. , powders such as aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers made of spherical or pulverized powders. can be done.
  • the amount of the inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. be.
  • the curable resin composition of the present invention can contain known additives as necessary.
  • additives that can be used include polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, silicone gels, silicone oils, fillers such as silane coupling agents. Coloring agents such as surface treatment agents for materials, release agents, carbon black, phthalocyanine blue, and phthalocyanine green.
  • the amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less per 100 parts by mass of the curable resin composition.
  • Particularly preferred components for these additives include polybutadiene, modified products thereof, and butadiene-based thermoplastic elastomers. Details regarding these components are provided below.
  • Styrene-butadiene rubber includes, for example, RICON-100, RICON-181, RICON-184 (all manufactured by Clay Valley), and polybutadiene includes B-1000, B-2000, B-3000 ( All of them are manufactured by Nippon Soda Co., Ltd.) and the like. These may be used alone or in combination of two or more.
  • the weight average molecular weight of polybutadiene and styrene-butadiene rubber is preferably from 500 to 10,000, more preferably from 750 to 7,500, still more preferably from 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during preparation of the prepreg. Above the upper limit of the above range, compatibility with other curable resins deteriorates.
  • Butadiene-based thermoplastic elastomer 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, both manufactured by Kuraray Co., Ltd.), SEEPS (Styrene-ethylene/ethylene/propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, both of Kuraray Co., Ltd.
  • SEBS styrene-ethylene/butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L; all manufactured by Kuraray Co., Ltd.
  • SEEPS-OH styrene-ethylene/ethylene/propylene-styrene block copolymer Compounds having a hydroxyl group at the end of the polymer: Septon HG252 manufactured by Kuraray Co., Ltd.
  • SIS styrene-isoprene-styrene block copolymers: Septon 5125, Septon 5127 manufactured by Kuraray Co., Ltd.
  • hydrogenated SIS water Added styrene-isoprene-styrene block copolymer: Hybler 7125F, Hybler 7311F (both manufactured by Kuraray Co., Ltd.) and the like.
  • butadiene-based thermoplastic elastomers those having no unsaturated bonds are preferred because they have higher heat resistance and are less susceptible to oxidation deterioration.
  • the weight average molecular weight of the butadiene-based thermoplastic elastomer is not particularly limited as long as it is 10,000 or more.
  • the compatibility with oligomer components of about 5,000 deteriorates, making it difficult to ensure mixing and solvent stability.
  • the curable resin composition of the present invention is obtained by uniformly mixing the above-mentioned respective components in a predetermined ratio, usually precured at 130 to 180 ° C. for 30 to 500 seconds, and further cured at 150 to 200 ° C. After curing for 2 to 15 hours at , the curing reaction proceeds sufficiently to obtain the cured product of the present invention. It is also possible to uniformly disperse or dissolve the components of the curable resin composition in a solvent or the like, remove the solvent, and then cure the composition.
  • the curable resin composition of the present invention thus obtained has moisture resistance, heat resistance, and high adhesiveness. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance and high adhesion. Specifically, it is useful as an insulating material, laminate (printed wiring board, BGA substrate, build-up substrate, etc.), sealing material, resist, and all other materials for electrical and electronic parts. In addition to molding materials and composite materials, it can also be used in fields such as paint materials, adhesives, and 3D printing. Particularly in semiconductor encapsulation, solder reflow resistance is beneficial.
  • a semiconductor device has one sealed with the curable resin composition of the present invention.
  • 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. (think quad flat package) and the like.
  • the method of preparing the curable resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be prepolymerized.
  • the curable resin of the present invention is prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent.
  • a curing agent such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives may be added to form a prepolymer. good.
  • Mixing or prepolymerization of each component is carried out by using, for example, an extruder, kneader, rolls, etc. in the absence of a solvent, and by using a reactor equipped with a stirrer in the presence of a solvent.
  • the components are kneaded at a temperature within the range of 50 to 100° C. using a device such as a kneader, a roll, or a planetary mixer to obtain a uniform resin composition.
  • the obtained resin composition is pulverized and then molded into a cylindrical tablet by a molding machine such as a tablet machine, or formed into granular powder or a powdery molding, or these compositions are placed on a surface support. It can also be melted and molded into a sheet having a thickness of 0.05 mm to 10 mm to form a curable resin composition molding.
  • the obtained molded article becomes a non-sticky molded article at 0 to 20.degree.
  • the resulting molded product can be molded into a cured product using a transfer molding machine or a compression molding machine.
  • An organic solvent can be added to the curable resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish).
  • the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to form a varnish.
  • a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.
  • Polyester fiber, polyamide fiber, alumina fiber, paper, etc. is impregnated into a base material and heat-dried to obtain a prepreg, which is hot-press molded to obtain a cured product of the curable resin composition of the present invention. .
  • the solvent is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, it is possible to obtain a curable resin-cured product containing carbon fibers by, for example, the RTM method.
  • the curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and the like in the B-stage.
  • a film-type resin composition is obtained by applying the curable resin composition of the present invention as the curable resin composition varnish on a release film, removing the solvent under heating, and then performing B-stage. It is obtained as a sheet-like adhesive by This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.
  • a prepreg can be obtained by heating and melting the curable resin composition of the present invention, reducing the viscosity, and impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers with the melted resin composition.
  • reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers with the melted resin composition.
  • Specific examples thereof 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, inorganic fibers other than glass, and poly paraphenylene terephthalamide (Kevlar®, manufactured by DuPont), wholly aromatic polyamides, polyesters; and organic fibers such as polyparaphenylene benzoxazole, polyimides and carbon fibers, but are particularly limited to these.
  • the shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. Plain weave, Nanako weave, twill weave, and the like are known as weaving methods of woven fabric, and it is possible to appropriately select and use from these known methods depending on the intended use and performance.
  • a woven fabric subjected to opening treatment or a glass woven fabric surface-treated with a silane coupling agent or the like is preferably used.
  • the thickness of the base material is not particularly limited, it is preferably about 0.01 to 0.4 mm.
  • a prepreg can also be obtained by impregnating reinforcing fibers with the varnish and heating and drying the varnish.
  • the laminate of the present embodiment includes one or more prepregs.
  • the laminate is not particularly limited as long as it comprises one or more prepregs, and may have any other layers.
  • a method for producing a laminate generally known methods can be appropriately applied, and there is no particular limitation. 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 above prepregs are laminated and heat-pressed to form a laminate. Obtainable.
  • the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C.
  • the pressure to be applied is not particularly limited, but if the pressure is too high, it will be difficult to adjust the solid content of the resin in the laminate and the quality will not be stable. 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable, because it deteriorates.
  • the laminate of the present embodiment can be suitably used as a metal-foil-clad laminate described later by including a layer made of metal foil. After cutting the prepreg into a desired shape and laminating it with copper foil or the like if necessary, the curable resin composition is heat-cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. Electrical and electronic laminates (printed wiring boards) and carbon fiber reinforcing materials can be obtained.
  • the cured product of the present invention can be used for various purposes such as molding materials, adhesives, composite materials, and paints. Since the cured product of the curable resin composition according to the present invention exhibits excellent heat resistance and dielectric properties, it can be used as a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, a sealing material for organic EL elements, and a printed wiring board. , electrical and electronic parts such as build-up laminates, and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.
  • Example 1 Thermometer, condenser, flask equipped with a stirrer 2-bromoethylbenzene (manufactured by Tokyo Kasei Co., Ltd.) 37.0 parts, 4,4'-dichloro-p-xylene (manufactured by Tokyo Kasei Co., Ltd.) 17.5 parts, diphenylmethane 8.4 parts and 3.2 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and reacted at 130° C. for 5 hours. After standing to cool, it was extracted with 200 parts of toluene, and the organic layer was washed 5 times with 100 parts of water.
  • FIG. 2 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a bromoethyl group was observed at 3.05-3.60 ppm in the 1 H-NMR chart.
  • Example 2 BEB-1 obtained in Example 1 (25.0 parts), 20 parts of toluene, 60 parts of dimethyl sulfoxide, 4-hydroxy-2,2,6,6 in a flask equipped with a thermometer, a condenser, and a stirrer 0.0125 parts of tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 12.0 parts of a 50 wt % sodium hydroxide aqueous solution were added and reacted at 40° C. for 6 hours. Thereafter, 100 parts of water was added and the organic layer was washed with water to remove the produced salt. Furthermore, the organic layer was returned to the reaction vessel again and reacted at 40° C. for 1 hour.
  • Example 3 A thermometer, a cooling tube, a flask equipped with a stirrer, 37.0 parts of 2-bromoethylbenzene (manufactured by Tokyo Kasei Co., Ltd.), 4,4'-dichloro-p-xylene (manufactured by Tokyo Kasei Co., Ltd.) 17.5 parts, diphenyl ether 8.5 parts and 3.2 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and reacted at 130° C. for 5 hours. After standing to cool, it was extracted with 200 parts of toluene, and the organic layer was washed 5 times with 100 parts of water.
  • 2-bromoethylbenzene manufactured by Tokyo Kasei Co., Ltd.
  • 4,4'-dichloro-p-xylene manufactured by Tokyo Kasei Co., Ltd.
  • methanesulfonic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • FIG. 6 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a bromoethyl group was observed at 3.00-3.60 ppm in the 1 H-NMR chart.
  • Example 4 BEB-2 obtained in Example 3 (25.0 parts), 20 parts of toluene, 60 parts of dimethyl sulfoxide, 4-hydroxy-2,2,6,6 in a flask equipped with a thermometer, a condenser, and a stirrer 0.0125 parts of tetramethylpiperidine-1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 12.0 parts of a 50 wt % sodium hydroxide aqueous solution were added and reacted at 40° C. for 6 hours. Thereafter, 100 parts of water was added and the organic layer was washed with water to remove the produced salt. Furthermore, the organic layer was returned to the reaction vessel again and reacted at 40° C. for 1 hour.
  • ⁇ Heat resistance test> Glass transition temperature: measured by a dynamic viscoelasticity tester, the temperature at which tan ⁇ reaches its maximum value.
  • thermometer A thermometer, a condenser, a flask equipped with a stirrer, 296 parts of 2-bromoethylbenzene (manufactured by Tokyo Kasei Co., Ltd.), ⁇ , ⁇ '-dichloro-p-xylene (manufactured by Tokyo Kasei Co., Ltd.) 70 parts, methanesulfonic acid (Tokyo (manufactured by Kasei Co., Ltd.) was charged and reacted at 130° C. for 8 hours. After allowing to cool, the mixture was neutralized with an aqueous sodium hydroxide solution, extracted with 1200 parts of toluene, and the organic layer was washed 5 times with 100 parts of water.
  • 2-bromoethylbenzene manufactured by Tokyo Kasei Co., Ltd.
  • ⁇ , ⁇ '-dichloro-p-xylene manufactured by Tokyo Kasei Co., Ltd.
  • methanesulfonic acid Tokyo
  • a GPC chart of the obtained compound is shown in FIG.
  • the repeating unit n calculated from the area % of the GPC chart was 1.7.
  • 1 H-NMR data (DMSO-d6) of the obtained compound is shown in FIG.
  • Signals derived from vinyl groups were observed at 5.10-5.30 ppm, 5.50-5.85 ppm, and 6.60-6.80 ppm in the 1 H-NMR chart.
  • Examples 8 and 9, Comparative Example 2 Two parts each of the olefin resins (O-1 and O-2) obtained in Examples 2 and 4 and the olefin resin (O-3) obtained in Reference Example 2 were weighed out. After applying each olefin resin to the matte surface of a low-roughness copper foil (T-4X, thickness 18 ⁇ m) manufactured by Fukuda Metal Copper Foil, the central part of the cushion paper was cut out 15 cm square (after curing, the film thickness will be 300 ⁇ m. Thickness) was used as a spacer, and a low-roughness copper foil (T-4X, thickness 18 ⁇ m) manufactured by Fukuda Metal Copper Foil was overlaid thereon so that the matte surface was in contact with the resin. It was cured at 220° C. for 1 hour while applying a vacuum pressure of 1 MPa using a vacuum press. Table 2 shows the results of a copper foil adhesion test using this sample.
  • Table 2 shows that Examples 8 and 9 are superior to Comparative Example 2 in adhesion.
  • the compound of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor sealing material), a laminate (such as a printed wiring board, a BGA substrate, and a build-up substrate), an adhesive (such as a conductive adhesive), or It is useful for various composite materials such as CFRP, paints, and 3D printing.

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WO2024203532A1 (ja) * 2023-03-28 2024-10-03 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れらの硬化物
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CN121002074A (zh) * 2023-06-07 2025-11-21 日本化药株式会社 硬化性树脂组合物及其硬化物
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TWI822584B (zh) * 2022-12-21 2023-11-11 台光電子材料股份有限公司 樹脂組合物及其製品
WO2024203532A1 (ja) * 2023-03-28 2024-10-03 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れらの硬化物
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CN121002074A (zh) * 2023-06-07 2025-11-21 日本化药株式会社 硬化性树脂组合物及其硬化物
WO2025004958A1 (ja) * 2023-06-27 2025-01-02 四国化成工業株式会社 トリス［（エテニルフェニル）メチル］ベンゼン類、その合成方法およびその利用

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