WO2022234829A1 - マレイミド樹脂、硬化性樹脂組成物およびその硬化物 - Google Patents

マレイミド樹脂、硬化性樹脂組成物およびその硬化物 Download PDF

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WO2022234829A1
WO2022234829A1 PCT/JP2022/019408 JP2022019408W WO2022234829A1 WO 2022234829 A1 WO2022234829 A1 WO 2022234829A1 JP 2022019408 W JP2022019408 W JP 2022019408W WO 2022234829 A1 WO2022234829 A1 WO 2022234829A1
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parts
compound
acid
formula
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 KR1020237038156A priority Critical patent/KR102772152B1/ko
Priority to CN202280033186.3A priority patent/CN117279962B/zh
Priority to JP2022564751A priority patent/JP7208705B1/ja
Publication of WO2022234829A1 publication Critical patent/WO2022234829A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/08—Anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a maleimide resin having a specific structure, a curable resin composition, and a cured product thereof, and includes semiconductor sealing materials, printed wiring boards, electric and electronic parts such as build-up laminates, carbon fiber reinforced plastics, Lightweight high-strength materials such as glass fiber reinforced plastics are suitable 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 a maleimide resin, a curable resin composition, and a cured product thereof that exhibits excellent heat resistance and electrical properties and has good curability. With the goal.
  • a maleimide resin having a specific structure and a cured product of the curable resin composition thereof are excellent in heat resistance and low dielectric properties, and have completed the present invention. I came to complete it.
  • the present invention relates to the following [1] to [10].
  • "(numerical value 1) to (numerical value 2)" indicate that upper and lower limits are included.
  • [1] A maleimide resin obtained by reacting a styrene-maleic acid copolymer, a compound containing two or more amino groups in the molecule, and maleic anhydride.
  • [2] The maleimide resin according to [1] above, which has repeating units represented by the following formulas (a) and (b).
  • X represents an arbitrary organic group.
  • m and n are the average values of the number of repetitions, and 1 ⁇ m ⁇ 1000 and 1 ⁇ n ⁇ 1000.
  • (a) and (b) are respectively It is connected with *, and the repeat position can be random.)
  • [3] The maleimide resin according to the preceding item [2], wherein X in the formula (b) is one or more of the following formulas (A) to (P).
  • R represents a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 0 to 4, p represents a number of 1 to 20, * indicates a bonding position.
  • X in formula (b) is any one or more of formulas (A) to (F).
  • the compound containing two or more amino groups in the molecule is any one or more selected from the group consisting of amine compounds represented by the following formulas (1) to (5) and dimer diamine [1] ]
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • each R exists independently and represents a hydrocarbon group having 1 to 3 carbon atoms, p is the average number of repetitions, and 0 ⁇ p ⁇ 20.
  • each R exists independently and represents a hydrocarbon group having 1 to 3 carbon atoms
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • [6] A curable resin composition containing the maleimide resin according to any one of [1] to [5] above.
  • the maleimide resin of the present invention has excellent curability, and its cured product has excellent properties such as high heat resistance and low dielectric properties. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, and the like.
  • FIG. 1 shows a GPC chart of Synthesis Example 1.
  • the HPLC chart of Synthesis Example 1 is shown.
  • 1 H-NMR chart of Synthesis Example 1 is shown.
  • 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.
  • the GPC chart of Example 4 is shown.
  • the GPC chart of Example 5 is shown.
  • 1 H-NMR chart of Example 5 is shown.
  • the GPC chart of Example 6 is shown.
  • 1 shows a 1 H-NMR chart of Synthesis Example 6.
  • FIG. The GPC chart of Example 7 is shown.
  • the GPC chart of Example 8 is shown.
  • the GPC chart of Example 9 is shown.
  • the GPC chart of Example 10 is shown. 1 H-NMR chart of Example 10 is shown. The GPC chart of Example 11 is shown. 1 H-NMR chart of Example 11 is shown. The GPC chart of Example 12 is shown. 1 H-NMR chart of Example 12 is shown. The GPC chart of Example 13 is shown. 1 H-NMR chart of Example 13 is shown. The GPC chart of Example 14 is shown. 1 H-NMR chart of Example 14 is shown. The GPC chart of Example 15 is shown. 1 H-NMR chart of Example 15 is shown.
  • the maleimide resin of the present invention is obtained by reacting a styrene-maleic acid copolymer, a compound containing two or more amino groups in the molecule, and maleic anhydride.
  • the maleimide resin of the present invention preferably has repeating units of the following formulas (a) and (b).
  • X represents any organic group.
  • m and n are the average values of the number of repetitions, and 1 ⁇ m ⁇ 1000 and 1 ⁇ n ⁇ 1000. (a) and (b) are each connected by *, and the repeat position may be random.
  • m is usually 1 ⁇ m ⁇ 1000, preferably 2 ⁇ m ⁇ 750, and preferably 3 ⁇ m ⁇ 500.
  • n is usually 1 ⁇ n ⁇ 1000, preferably 1 ⁇ n ⁇ 500, more preferably 1.1 ⁇ n ⁇ 100, particularly preferably 1.1 ⁇ n ⁇ 20 . Since the values of m and n are derived from the raw material styrene-maleic acid copolymer, they can be obtained from the acid value thereof.
  • the preferred range of the molecular weight of the raw styrene-maleic acid copolymer is 200 or more and less than 50,000.
  • the target compound does not volatilize in the solvent distillation step.
  • X is preferably one or more of the following formulas (A) to (P), more preferably any one of the following formulas (A) to (F). , the following formula (B) is particularly preferred.
  • R represents a hydrocarbon group having 1 to 10 carbon atoms.
  • a represents an integer of 0 to 4;
  • p is the average number of repetitions, and 0 ⁇ p ⁇ 20. * indicates the binding position.
  • the average value p of the number of repetitions of formula (E) is the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (E) or the area % of slice data of each peak (detection instrument: differential refractive index detector) and the like.
  • R is usually a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms. It is a hydrocarbon group. Hydrocarbons in which R has 10 or less carbon atoms are less susceptible to molecular vibration when exposed to high frequency waves, and are therefore excellent in electrical properties.
  • the styrene-maleic acid copolymer which is the raw material for the maleimide resin of the present invention, is obtained by copolymerizing styrene and maleic anhydride.
  • the polymerization method any known method other than radical polymerization, coordination polymerization, and various living polymerizations may be used. For example, by reacting styrene and maleic anhydride in toluene in the presence of a radical polymerization initiator, Obtainable.
  • the polymer obtained may be a random polymer or a periodic copolymer, or may be a block polymer or an alternating copolymer.
  • the stereoregularity of the polystyrene segment may be syndiotactic, atactic, isotactic, or the like.
  • the weight average molecular weight (Mw) is preferably 500 to 50,000, more preferably 750 to 40,000, even more preferably 1,000 to 30,000, and particularly preferably 1,500 to 20,000. If the molecular weight is less than 500, the target product is likely to volatilize and the weight of the resin component is reduced during heating, making it difficult to apply to the manufacturing process of the substrate material. On the other hand, if the molecular weight is more than 30,000, it becomes difficult to expand sales during production, and it becomes difficult to purify by washing with water.
  • Any known amine compound may be used as the compound having two or more amino groups in the molecule, which is the starting material for the maleimide resin of the present invention.
  • amine compounds represented by the following formulas (A′) to (P′) methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, dimerdiamine, 1,3 - Aliphatic diamine compounds such as bisaminomethylcyclohexane, norbornanediamine, isophoronediamine and bisaminomethyltricyclodecane.
  • the dimer diamine is a diamine in which the two terminal carboxylic acid groups (--COOH) of the dimer acid are substituted with primary aminomethyl groups (--CH.sub.2--NH.sub.2) or amino groups ( --NH.sub.2 ).
  • a known commercial product may be used as the dimer diamine.
  • Commercially available products include Priamine (registered trademark) manufactured by Croda Japan.
  • the compound having two or more amino groups in the molecule exemplified above is preferably dimer diamine or any one or more of the following formulas (A') to (P'), and the following formula (A') (F') is more preferred, and formula (B') below is particularly preferred. This is because heat resistance and solvent solubility can be improved by using an amine compound having a molecular weight distribution. In addition, these may be used independently and may be used together.
  • R represents a hydrocarbon group having 1 to 10 carbon atoms.
  • a represents an integer of 0 to 4;
  • p is the average number of repetitions, and 0 ⁇ p ⁇ 20.
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • the average value p of the number of repetitions of formula (E') and the average value n of the number of repetitions of formulas (A'), (B'), (C'), (D'), and (F') are Value of number average molecular weight (Mn) obtained by GPC measurement of compounds represented by formulas (A') to (F'), area % of slice data of each peak (detector: differential refractive index detector), etc. can be calculated from
  • 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 10 or less carbon atoms are less susceptible to molecular vibration when exposed to high frequency waves, and are therefore excellent in electrical properties. Moreover, it is preferable that p satisfies 1 ⁇ p ⁇ 20 and n satisfies 1 ⁇ n ⁇ 5.
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • the average value n of the number of repetitions in formula (1) is the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (1) or the area % of slice data of each peak (detector : differential refractive index detector).
  • each R exists independently and represents a hydrocarbon group having 1 to 3 carbon atoms
  • p is the average number of repetitions
  • 0 ⁇ p ⁇ 20 The average value p of the number of repetitions in formula (2) is the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (2) or the area % of slice data of each peak (detector : differential refractive index detector).
  • the above formula (F') is particularly preferably when a is 2 and n is 0, that is, the following formula (3), or when a is 0, that is, the following formula (4).
  • each R exists independently and represents a hydrocarbon group having 1 to 3 carbon atoms.
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • the average value n of the number of repetitions in formula (4) is the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (4) or the area % of slice data of each peak (detector : differential refractive index detector).
  • a is 0 in the above formula (C'), that is, the following formula (5).
  • n is the average number of repetitions, and 1 ⁇ n ⁇ 5.
  • the average value n of the number of repetitions in formula (5) is the value of the number average molecular weight (Mn) obtained by GPC measurement of the compound represented by formula (5) or the area % of slice data of each peak (detector : differential refractive index detector).
  • the method for producing the maleimide resin of the present invention is not particularly limited, but it can be derived from a styrene-maleic acid copolymer, a compound having two or more amino groups in the molecule, and maleic anhydride. Specifically, a styrene-maleic acid copolymer and a compound having two or more amino groups in the molecule are imidized in a solvent in the presence of a catalyst. can be obtained by additionally adding and maleimidating.
  • the amino group of the amine compound is excessively charged with respect to 1 mol of the acid anhydride contained in the styrene-maleic acid copolymer, thereby suppressing gelation due to three-dimensional cross-linking during the reaction step. can be prevented.
  • the preferred range of the value ( ⁇ / ⁇ ) obtained by dividing the number of moles ( ⁇ ) of the amino group of the raw material amine by the number of moles ( ⁇ ) of the acid anhydride of the styrene-maleic acid copolymer is 1.1. ⁇ 20, preferably 1.1-15, more preferably 1.1-10. If the amine content is less than the above range, gelation will occur, making production difficult.
  • 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 and cyclopentanone are included, but are not limited to these, and two or more kinds 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.
  • an aprotic polar solvent it is preferable to use one having a boiling point higher than that of the water-insoluble solvent used in combination.
  • catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, A solid acid such as silica alumina, an acidic ion exchange resin, or the like can be used. These may be used alone or in combination of two or more.
  • the amount of the catalyst used is generally 0.1-0.8 mol, preferably 0.2-0.7 mol, per 1 mol of the amino group of the amine compound used. 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.
  • a basic co-catalyst such as triethylamine can be used alone or in combination.
  • the extraction step may be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide.
  • an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon solvent such as cyclohexane or toluene may be used in combination.
  • the organic layer is washed with water until the waste water becomes neutral, and the solvent is distilled off using an evaporator or the like to obtain the desired maleimide resin having a polystyrene structure in the molecule.
  • the maleimide resin having repeating units of the formulas (a) and (b) can be represented by the following formula (6).
  • X represents any organic group.
  • m and n are the average values of the number of repetitions, and 1 ⁇ m ⁇ 1000 and 1 ⁇ n ⁇ 1000. Since the values of m and n are derived from the raw material styrene-maleic acid copolymer, they can be obtained from the acid value thereof. Although each repeating unit is shown in a particular order for convenience of description, each repeating position may be random.
  • the curable composition of the invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, the storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, fluidity can be easily ensured, the ability to impregnate glass cloth or the like is not impaired, and B-stage processing such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination are likely to occur in the lamination process.
  • 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 maleimide resin of the present invention 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.
  • 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.
  • 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 maleimide resin 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 or less by mass, more preferably 5 times or less, and particularly preferably 3 times or less by mass, that of the maleimide resin of the present invention.
  • the lower limit is preferably 0.5 times by mass or more, more preferably 1 time by mass or more. If it is 10 times by mass or less, the effect of the heat resistance and dielectric properties of the maleimide resin of the present invention 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
  • Any known polyphenylene ether compound may be used, but from the viewpoint of heat resistance and electrical properties, it is preferably a polyphenylene ether compound having an ethylenically unsaturated double bond. or a polyphenylene ether compound having a styrene structure is more preferred.
  • Commercially available products include SA-9000-111 (polyphenylene ether compound having a methacryl group, manufactured by SABIC) and OPE-2St 1200 (polyphenylene ether compound having a styrene structure, manufactured by Mitsubishi Gas Chemical Co.).
  • the number average molecular weight (Mn) of the polyphenylene ether compound is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, and even more preferably from 2,000 to 4,000. If the molecular weight is less than 500, there is a tendency that the heat resistance of the cured product is insufficient. On the other hand, when the molecular weight is more than 5000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, so that molding defects tend to occur. In addition, reactivity also decreases, the curing reaction takes a long time, unreacted substances increase without being incorporated into the curing system, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product decreases.
  • the polyphenylene ether compound has a number average molecular weight of 500 to 5000, excellent heat resistance and moldability can be exhibited 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 may be obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. Radical polymerizability may also be imparted by reacting these raw materials with a compound having an ethylenically unsaturated double bond such as methacryl chloride, acryl chloride, chloromethylstyrene, or the like.
  • the polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound portion in a solvent such as toluene in the presence of a phenol compound and a radical initiator to cause a redistribution reaction.
  • the polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain. It is preferable because functional groups can be introduced to both ends of the molecular chain even after modification with a compound having a polyunsaturated double bond.
  • a polyphenylene ether compound obtained by a polymerization reaction is also preferable because it exhibits excellent fluidity.
  • the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions and the like in the case of the polyphenylene ether compound obtained by the polymerization reaction.
  • the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, it is conceivable to adjust the blending amount of the phenolic compound used in the redistribution reaction. That is, the larger the amount of the phenolic compound compounded, the lower the molecular weight of the obtained polyphenylene ether compound.
  • poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction.
  • the phenolic compound used in the redistribution reaction is not particularly limited, but for example, polyfunctional phenols having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolak, cresol novolak, etc. compounds are preferably used. These may be used alone or in combination of two or more.
  • the content of the polyphenylene ether compound is not particularly limited, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable resin components.
  • the content of the polyphenylene ether compound is 10 to 90% by mass, not only is it excellent in heat resistance, etc., but it is also preferable in terms of obtaining a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.
  • 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 resin 1 selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.), lactams ( ⁇ -caprolactam, ⁇ -undecanelactam, ⁇ -laurolactam) A polymer containing at least one species as main raw materials; or a polymer containing one or more diamines and one or more dicarboxylic acids as main raw materials.
  • Diamines ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine , hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane; cyclohexanediamine, bis - Alicyclic diamines such as (4-aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine; Di
  • Polyimide resin a polycondensate of the above diamine and tetracarboxylic dianhydride.
  • Tetracarboxylic dianhydride 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic acid 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′-diphenylsulfonetetracarboxylic dianhydride, 2 ,2′,3,3′
  • 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 can be used as a curing agent for a curable resin other than the maleimide resin of the present invention, such as an epoxy resin, if necessary.
  • 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.
  • a hindered amine light stabilizer HALS
  • 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-
  • HALS hindered amine light stabilize
  • 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.
  • Polybutadiene and modified products thereof polyphenylene ether, polystyrene, polyethylene, fluororesins, and the like are preferred from the viewpoint of low water absorption and electrical properties.
  • Polybutadiene and its modified products are preferred from the viewpoint of electrical properties, adhesion and low water absorption.
  • butadiene-based thermoplastic elastomers such as styrene-butadiene copolymers (SBR: RICON-100, RICON-181, RICON-184, all manufactured by Clay Valley, etc.), acrylonitrile-butadiene copolymers; styrene-butadiene Styrene copolymer (SBS), hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer (SIS), hydrogenated styrene isoprene styrene copolymer, hydrogenated styrene (butadiene/isoprene) styrene copolymer, etc.
  • SBR styrene-butadiene copolymers
  • SBS styrene-butadiene Styrene copolymer
  • SIS styrene
  • Styrene-based thermoplastic elastomers and the like are included. These styrenic thermoplastic elastomers may be used alone or in combination of two or more. Among these high molecular weight substances, styrene-butadiene-styrene copolymer, hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene/isoprene) styrene.
  • Styrenic thermoplastic elastomers such as copolymers are preferred, particularly styrene-isoprene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, hydrogenated styrene (butadiene/isoprene)-styrene copolymers. Coalescing is more preferred because it has higher heat resistance and is less prone to oxidative degradation.
  • the compatibility with the polyphenylene ether compound, low molecular weight components with a weight average molecular weight of about 50 to 1000, and oligomer components with a weight average molecular weight of about 1000 to 5000 will deteriorate, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.
  • compounds containing heteroatoms such as oxygen and nitrogen such as bismaleimide and polymaleimide
  • they are mainly composed of hydrocarbons. It is difficult to ensure compatibility with low-polarity compounds such as compounds or compounds consisting only of hydrocarbons.
  • the maleimide resin of the present invention does not itself have a skeleton design that actively introduces heteroatoms such as oxygen and nitrogen (there are few polar groups). It also has excellent compatibility with compounds composed only of hydrocarbons.
  • 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 where moisture resistance, heat resistance and high adhesion are required. 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 maleimide resins of the present invention are 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 for prepolymerization. .
  • 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.
  • it is a liquid composition, it is also possible to obtain a curable resin cured product containing carbon fibers by, for example, the RTM (Resin Transfer Molding) 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.
  • GPC Gal permeation chromatography
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • GPC DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
  • Linking eluent Tetrahydrofuran Flow rate: 0.5 ml/min.
  • aromatic amine resin (A1) represented by the following formula (1-a).
  • the aromatic amine resin (A1) had an amine equivalent of 185 g/eq and a softening point of 58.7°C.
  • RI GPC analysis
  • Example 1 Thermometer, cooling tube, 75 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-69, manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000) 11.2 parts, 14.8 parts of the aromatic amine (A1) obtained in Synthesis Example 1 and 0.6 parts of methanesulfonic acid were charged and reacted at 110° C. for 4 hours. After standing to cool, 10.3 parts of maleic anhydride was added, and the reaction was continued under reflux for 16 hours. After allowing to cool, the organic layer was washed 5 times with 100 parts of water.
  • RK-69 styrene-maleic acid copolymer manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000
  • FIG. 4 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 5 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 7.08 ppm (s) in the 1 H-NMR chart.
  • Example 2 A flask equipped with a thermometer, a condenser, and a stirrer was charged with 75 parts of toluene, 11.2 parts of a styrene-maleic acid copolymer (SMA EF80, manufactured by Clay Valley, acid value: 120, Mw: 14400), Synthesis Example 1. 14.8 parts of the aromatic amine (A1) obtained in 1. and 0.6 parts of methanesulfonic acid were charged and reacted at 110° C. for 4 hours. After standing to cool, 8.8 parts of maleic anhydride was added, and the reaction was continued under reflux for 16 hours. After allowing to cool, the organic layer was washed 5 times with 100 parts of water.
  • SMA EF80 styrene-maleic acid copolymer
  • FIG. 6 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 7 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 7.08 ppm (s) in the 1 H-NMR chart.
  • Example 3 Thermometer, cooling tube, 75 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-69, manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000) 11.2 parts, 11.2 parts of the aromatic amine (A1) obtained in Synthesis Example 1 and 0.6 parts of methanesulfonic acid were charged and reacted at 110° C. for 3 hours. After standing to cool, 7.4 parts of maleic anhydride was added and the reaction was continued under reflux for 16 hours. After standing to cool, 50 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 26.3 parts of the target compound (M-3) was obtained as a brown solid resin (Mn: 1378, Mw: 2875).
  • FIG. 8 shows a GPC chart of the obtained compound during the reaction.
  • Example 4 A flask equipped with a thermometer, a condenser, and a stirrer was charged with 75 parts of toluene, 9.4 parts of a styrene-maleic acid copolymer (SMA EF80, manufactured by Clay Valley, acid value: 120, Mw: 14400), Synthesis Example 1. 7.4 parts of the aromatic amine (A1) obtained in 1. and 0.3 parts of methanesulfonic acid were charged and reacted at 110° C. for 2 hours. After standing to cool, 2.9 parts of maleic anhydride was added, and the reaction was continued under reflux for 16 hours. After standing to cool, 100 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, the target compound (M-4) was obtained as a brown solid resin (Mn: 2186, Mw: 14502).
  • FIG. 9 shows a GPC chart of the obtained compound during the reaction.
  • Example 5 Thermometer, cooling tube, 75 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-69, manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000) 11.2 parts, 11.8 parts of the aromatic amine (A1) obtained in Synthesis Example 1, 5.1 parts of dimer diamine (Preamine: manufactured by Croda Japan), and 0.68 parts of methanesulfonic acid were charged and reacted at 110°C for 4 hours. rice field. After standing to cool, 10.3 parts of maleic anhydride was added, and the reaction was continued under reflux for 16 hours.
  • RK-69 styrene-maleic acid copolymer
  • A1 aromatic amine
  • Preamine manufactured by Croda Japan
  • methanesulfonic acid were charged and reacted at 110°C for 4 hours. rice field. After standing to cool, 10.3 parts of maleic anhydride was added,
  • FIG. 10 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 11 shows the 1H-NMR chart (deuterium chloroform) of the obtained compound. Signals derived from the maleimide group were observed at 6.82 (s) and 6.85 ppm (s) in the 1H-NMR chart.
  • Example 6 Thermometer, cooling tube, 75 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-69, manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000) 11.2 parts, 5.4 parts of dimer diamine (Preamine: manufactured by Croda Japan) and 0.2 parts of methanesulfonic acid were charged and reacted at 110° C. for 3 hours. After standing to cool, 1.5 parts of maleic anhydride was added and the reaction was continued under reflux for 6 hours. After allowing to cool, the organic layer was washed 5 times with 100 parts of water.
  • RK-69 styrene-maleic acid copolymer manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000
  • Preamine manufactured by Croda Japan
  • methanesulfonic acid were charged and reacted at 110° C. for 3 hours. After standing to cool
  • FIG. 12 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 13 shows a 1H-NMR chart (heavy chloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.82 ppm (s) in the 1H-NMR chart.
  • Example 7 Thermometer, cooling pipe, 75 parts of toluene in a flask equipped with a stirrer, 9.4 parts of styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., acid value: 60, Mw: 10140), 11.2 parts of the aromatic amine (A1) obtained in Synthesis Example 1 and 0.5 parts of methanesulfonic acid were charged and reacted at 110° C. for 4 hours. After standing to cool, 7.4 parts of maleic anhydride was added and the reaction was continued under reflux for 16 hours. After standing to cool, 100 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 21.6 parts of the target compound (M-7) was obtained as a brown solid resin (Mn: 1834, Mw: 12628).
  • FIG. 14 shows a GPC chart of the obtained compound during the reaction.
  • Example 8 Thermometer, cooling pipe, 101 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) 18.7 parts, 14.9 parts of the aromatic amine (A1) obtained in Synthesis Example 1 and 0.6 parts of methanesulfonic acid were charged and reacted at 110° C. for 4 hours. After standing to cool, 8.8 parts of maleic anhydride was added, and the reaction was continued under reflux for 16 hours. After standing to cool, 50 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 35.2 parts of the target compound (M-8) was obtained as a brown solid resin (Mn: 2493, Mw: 19879). A GPC chart of the obtained compound is shown in FIG.
  • Example 9 Thermometer, cooling tube, 75 parts of toluene in a flask equipped with a stirrer, styrene-maleic acid copolymer (RK-69, manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000) 11.2 parts, 14.8 parts of the aromatic amine (A1) obtained in Synthesis Example 1 and 0.6 parts of methanesulfonic acid were charged and reacted at 110° C. for 4 hours. After standing to cool, 10.3 parts of maleic anhydride was added, and the reaction was continued under reflux for 28 hours. After allowing to cool, the organic layer was washed 5 times with 100 parts of water.
  • RK-69 styrene-maleic acid copolymer manufactured by Gifu Shellac Manufacturing Co., acid value: 50, Mw: 3000
  • FIG. 16 shows a GPC chart of the obtained compound during the reaction.
  • a maleimide resin (M-16) was obtained by completely distilling off at .
  • the resulting maleimide resin (M-3) had a softening point of 100° C. and an acid value of 9 mgKOH/g.
  • Example 10 75 parts of toluene, 25 parts of NMP, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) were placed in a flask equipped with a thermometer, a condenser, and a stirrer9. 4 parts, 14.9 parts of the aromatic amine (A2) obtained in Synthesis Example 2, and 0.3 parts of methanesulfonic acid were charged and reacted at 115° C. for 2 hours. After standing to cool, 4.4 parts of maleic anhydride was added, and the reaction was continued for 2 hours under reflux.
  • RK-42 styrene-maleic acid copolymer
  • FIG. 18 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.85 ppm (s) in the 1 H-NMR chart.
  • Example 11 75 parts of toluene, 25 parts of NMP, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) were placed in a flask equipped with a thermometer, a condenser, and a stirrer9. 4 parts, 9.4 parts of the aromatic amine (A3) obtained in Synthesis Example 3, and 0.25 parts of methanesulfonic acid were charged and reacted at 115° C. for 2 hours. After standing to cool, 4.4 parts of maleic anhydride was added, and the reaction was continued for 2 hours under reflux.
  • RK-42 styrene-maleic acid copolymer
  • FIG. 19 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 20 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.85 ppm (s) in the 1 H-NMR chart.
  • Example 12 75 parts of toluene, 25 parts of NMP, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) were placed in a flask equipped with a thermometer, a condenser, and a stirrer.18. 7 parts, 14.7 parts of the aromatic amine (A4) obtained in Synthesis Example 4, and 0.29 parts of methanesulfonic acid were charged and reacted at 111° C. for 8 hours. After allowing to cool, 8.8 parts of maleic anhydride was added, and the reaction was continued at 111°C for 2 hours.
  • RK-42 styrene-maleic acid copolymer
  • FIG. 21 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 22 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.87 ppm (s) in the 1 H-NMR chart.
  • A5 represented by the following formula (4-a) as a black liquid.
  • A5 has an amine equivalent of 100.6 g/eq. Met.
  • Example 13 75 parts of toluene, 25 parts of NMP, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) were placed in a flask equipped with a thermometer, a condenser, and a stirrer.18. 7 parts, 8.0 parts of the aromatic amine (A5) obtained in Synthesis Example 5, and 0.16 parts of methanesulfonic acid were charged and reacted at 120° C. for 2 hours. After allowing to cool, 8.8 parts of maleic anhydride was added, and the reaction was continued at 120°C for 6 hours.
  • RK-42 styrene-maleic acid copolymer
  • FIG. 23 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 24 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.85 ppm (s) in the 1 H-NMR chart.
  • Example 14 A thermometer, a cooling tube, a flask equipped with a stirrer, 71.6 parts of toluene, 75 parts of NMP, styrene-maleic acid copolymer (RK-42, Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) 13.9 parts, 11.8 parts of an amine resin represented by the following formula (5-a) synthesized according to Synthesis Example 2 of JP-A-2009-001783, and 0.25 parts of methanesulfonic acid were charged and heated at 100°C. The reaction was allowed to proceed for 8 hours. After allowing to cool, 6.6 parts of maleic anhydride was added, and the reaction was continued at 100°C for 2 hours.
  • FIG. 26 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.85 ppm (s) in the 1 H-NMR chart.
  • Example 15 75 parts of toluene, 25 parts of NMP, styrene-maleic acid copolymer (RK-42, manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140) were placed in a flask equipped with a thermometer, a condenser, and a stirrer.18. 7 parts, 11.3 parts of 4,4′-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 parts of methanesulfonic acid were charged and reacted at 120° C. for 2 hours.
  • RK-42 styrene-maleic acid copolymer manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 60, Mw: 10140
  • FIG. 27 shows a GPC chart of the obtained compound during the reaction.
  • FIG. 28 shows a 1 H-NMR chart (deuterochloroform) of the obtained compound. A signal derived from a maleimide group was observed at 6.87 ppm (s) in the 1 H-NMR chart.
  • Example 16-17 Comparative Examples 1-2
  • Each material was blended at the ratio shown in Table 1, kneaded in a mortar, poured into a mold, cured at 220° C. for 1 hour, and various tests were conducted.
  • Comparative Example 1 the proportions shown in Table 1 were blended, heated and melted and mixed in a metal container, poured into a mold as it was, transferred at 175 ° C., cured at 160 ° C. for 2 hours, and at 180 ° C. for 6 hours. let me
  • ⁇ Permittivity test/dielectric loss tangent test> Using a 10 GHz cavity resonator manufactured by AET Co., Ltd., a test was conducted by the cavity resonator perturbation method. The sample size was 1.7 mm wide by 100 mm long, and the thickness was 1.7 mm.
  • Dynamic viscoelasticity measuring instrument TA-instruments, DMA-2980 Measurement temperature range: -30 to 280°C Heating rate: 2°C/min Frequency: 10Hz
  • Test piece size A piece cut into 5 mm x 50 mm was used (thickness is about 800 ⁇ m)
  • NC-3000-L Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
  • GPH-65 Biphenyl aralkyl-type phenolic resin (manufactured by Nippon Kayaku Co., Ltd.)
  • 2E4MZ 2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Co., Ltd.)
  • Examples 16 and 17 were excellent in high heat resistance and low dielectric properties.
  • Example 18 to 31 Each material was blended in the ratio shown in Table 2, kneaded in a mortar, poured into a mold, cured at 220° C. for 1 hour, and various tests were performed.
  • ⁇ SA-9000 Polyphenylene ether compound (manufactured by SABIC)
  • Ricon-100 styrene-butadiene copolymer (manufactured by Clay Valley)
  • Perkadox 14 thermal radical polymerization initiator (manufactured by Kayaku Noorion Co., Ltd.)
  • the curable resin composition of the present invention and its cured product can be used as insulating materials for electrical and electronic parts (such as highly reliable semiconductor sealing materials), laminates (such as printed wiring boards, BGA substrates, and build-up substrates), and adhesives. (conductive adhesives, etc.), various composite materials including CFRP, paints, 3D printing, and other applications.
  • electrical and electronic parts such as highly reliable semiconductor sealing materials
  • laminates such as printed wiring boards, BGA substrates, and build-up substrates
  • adhesives conductive adhesives, etc.
  • various composite materials including CFRP, paints, 3D printing, and other applications.

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JP7534517B1 (ja) 2023-03-23 2024-08-14 日本化薬株式会社 マレイミド樹脂混合物、硬化性樹脂組成物およびその硬化物
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