WO2022181758A1 - 硬化性樹脂組成物、プリプレグおよびその硬化物 - Google Patents

硬化性樹脂組成物、プリプレグおよびその硬化物 Download PDF

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WO2022181758A1
WO2022181758A1 PCT/JP2022/007840 JP2022007840W WO2022181758A1 WO 2022181758 A1 WO2022181758 A1 WO 2022181758A1 JP 2022007840 W JP2022007840 W JP 2022007840W WO 2022181758 A1 WO2022181758 A1 WO 2022181758A1
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resin composition
curable resin
acid
compound
component
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French (fr)
Japanese (ja)
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允諭 関
昌典 橋本
大地 土方
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to CN202280008170.7A priority Critical patent/CN116615489A/zh
Priority to JP2022541780A priority patent/JP7157277B1/ja
Priority to KR1020237019433A priority patent/KR102821176B1/ko
Publication of WO2022181758A1 publication Critical patent/WO2022181758A1/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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs

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  • the present invention relates to a curable resin composition, a prepreg and a cured product thereof, and includes electrical and electronic components such as semiconductor sealing materials, printed wiring boards, and build-up laminates, carbon fiber reinforced plastics, glass fiber reinforced plastics, and the like.
  • electrical and electronic components such as semiconductor sealing materials, printed wiring boards, and build-up laminates, carbon fiber reinforced plastics, glass fiber reinforced plastics, and the like.
  • a lightweight high-strength material suitable for 3D printing applications.
  • Wiring boards using BT resin which is a resin in which a bisphenol A-type cyanate ester compound and a bismaleimide compound are combined, as in Patent Document 1, are excellent in heat resistance, chemical resistance, dielectric properties, etc. Although it has been widely used as a board, it needs to be improved in order to meet the above-mentioned higher performance requirements.
  • maleimide resins available on the market have significantly improved heat resistance compared to epoxy resins and the like that have been conventionally used for the above applications, and exhibit excellent dielectric properties in the high frequency range.
  • the heat-resistant maleimide resin has the drawbacks that it has low moisture resistance, is brittle due to its rigidity, and has low adhesion to copper foil.
  • maleimide resins such as those disclosed in Patent Documents 2 and 3 have been developed, but they are still insufficient.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a curable resin composition exhibiting excellent heat resistance, copper foil peel strength, dielectric properties, and moisture resistance, and a cured product thereof. do.
  • the cured product of a curable resin composition composed of a maleimide compound having a specific structure and a polyphenylene ether compound having an unsaturated double bond is heat resistant, copper foil
  • the inventors have found that the peel strength, dielectric properties, and moisture resistance are excellent, and have completed the present invention.
  • the present invention relates to the following [1] to [7].
  • [1] containing a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, wherein the weight ratio of component (A) and component (B) is 50/50
  • a curable resin composition that is ⁇ 5/95.
  • R represents a hydrogen atom or a methyl group.
  • m represents an integer of 0 to 3.
  • n is the number of repetitions, and its average value is 1 ⁇ n ⁇ 5.
  • a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond are contained, and the amount of component (B) is 0.00 per 1 equivalent of component (A).
  • a curable resin composition having an equivalent weight of 20 to 4.2.
  • R represents a hydrogen atom or a methyl group.
  • m represents an integer of 0 to 3.
  • n is the number of repetitions, and its average value is 1 ⁇ n ⁇ 5.
  • [3] The curable resin composition according to the preceding item [1] or [2], wherein the component (B) is a polyphenylene ether compound having a (meth)acrylic group.
  • [4] The curable resin composition according to any one of the preceding items [1] to [3], wherein the component (B) is a compound represented by the following formula (2) or a compound represented by the following formula (4) .
  • n is the number of repetitions, and the average value is 1 ⁇ n ⁇ 10.
  • n is the number of repetitions, and the average value is 1 ⁇ n ⁇ 10.
  • the cured product of the curable resin composition of the present invention has excellent heat resistance, copper foil peel strength, dielectric properties, and moisture resistance.
  • FIG. 1 is a GPC chart of Synthesis Example 1.
  • FIG. 2 is a GPC chart of Synthesis Example 2.
  • the curable resin composition of the invention is described below.
  • the curable resin composition of the present invention comprises a maleimide compound represented by the following formula (1) (hereinafter also referred to as component (A)) and a polyphenylene ether compound having an unsaturated double bond (hereinafter referred to as component (B ).
  • R represents a hydrogen atom or a methyl group.
  • m represents an integer of 0 to 3.n is the number of repetitions, and the average value is 1 ⁇ n ⁇ 5.
  • the compound represented by the above formula (1) is particularly preferably represented by the following formula (1-a).
  • n is calculated from the value of the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) of the maleimide resin, or from the area ratio of each of the separated peaks.
  • the solvent can be removed at a low temperature when the solid is taken out, the self-polymerization hardly occurs and the handling becomes easy.
  • the component (A) has good solvent solubility and can improve the dielectric properties of the cured product.
  • the softening point of component (A) is preferably 50°C to 150°C, more preferably 80°C to 120°C, still more preferably 90°C to 120°C, and particularly preferably 95°C to 120°C.
  • the melt viscosity at 150° C. is 0.05 to 100 Pa ⁇ s, preferably 0.1 to 40 Pa ⁇ s.
  • Component (A) can use an aromatic amine resin represented by the following formula (3) as a precursor.
  • R represents a hydrogen atom or a methyl group.
  • m represents an integer of 0 to 3.
  • n is the number of repetitions, and its average value is 1 ⁇ n ⁇ 5.
  • n 1 bodies, 1,3-bis(p-aminocumyl)benzene and 1,3-bis(o-aminocumyl)benzene, which have the same orientation with respect to two aniline molecules, have a symmetrical structure. It contains three isomers of a compound and an asymmetric structure compound with different orientations with respect to two aniline molecules such as 1-(o-aminocumyl)-3-(p-aminocumyl)benzene.
  • Patent Document 6 1,3-bis(p-aminocumyl)benzene is maleimidated to give N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bis.
  • a crystalline product is obtained by synthesizing maleimide, but it must be heated in order to dissolve it in a solvent, and if left at room temperature after heating, crystals will precipitate in several hours.
  • crystals may precipitate even when preparing a resin composition, and N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleimide
  • concentration the higher the probability of crystallization.
  • glass cloth or carbon fiber is impregnated with varnish to adhere the resin. Increasing the temperature accelerates the reaction of the composition and shortens the pot life of the varnish.
  • Acidic catalysts used in synthesizing the aromatic amine resin represented by the formula (3) include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, and methane.
  • acidic catalysts such as sulfonic acid.
  • protonic acids such as hydrochloric acid, p-toluenesulfonic acid and methanesulfonic acid are preferred. These may be used alone or in combination of two or more.
  • the amount of catalyst used is preferably 1 to 12% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 7% by weight, based on 100% by weight of the aniline used, and is more than 12% by weight. Therefore, there are few compounds with the desired asymmetric structure, and compounds with a symmetric structure are preferentially produced. On the other hand, if it is less than 1%, not only does the progress of the reaction slow down, but the reaction may not be completed in some cases, which is not preferable.
  • the reaction may be carried out using an organic solvent such as toluene, xylene, or the like, if necessary, or may be carried out without a solvent.
  • an organic solvent such as toluene, xylene, or the like
  • diisopropenylbenzene or di( ⁇ -hydroxyisopropyl)benzene is added, and then the temperature is raised while removing the solvent from the system to 140 to 190°C, preferably 160 to 190°C for 5 to 50 hours, preferably The reaction is carried out for 5-30 hours.
  • the reaction temperature is too high, the asymmetric structure is recombined after being formed, and the symmetric structure is preferentially formed, so that the desired solvent solubility and electrical properties cannot be exhibited.
  • water is by-produced when di( ⁇ -hydroxyisopropyl)benzene is used, it is removed from the system while being azeotroped with the solvent when the temperature is raised.
  • neutralize the acidic catalyst with an alkaline aqueous solution, add a water-insoluble organic solvent to the oil layer, repeat washing with water until the wastewater becomes neutral, and remove the solvent and excess aniline derivative under heating and reduced pressure.
  • activated clay or ion exchange resin is used, the reaction solution is filtered to remove the catalyst after completion of the reaction.
  • diphenylamine is produced as a by-product depending on the reaction temperature and the type of catalyst, and therefore it is preferable to remove it as necessary.
  • the diphenylamine derivative is removed to 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less, under high temperature and high vacuum, or by using means such as steam distillation.
  • Component (A) is an aromatic amine resin represented by the formula (3) obtained by the above process, and maleic acid or maleic anhydride (hereinafter also referred to as “maleic anhydride”) as a solvent and a catalyst. It can be obtained by addition or dehydration condensation reaction in the presence.
  • maleic anhydride maleic acid or maleic anhydride
  • a water-insoluble solvent because the solvent used in the reaction must remove the water generated during the reaction from the system.
  • 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; ketone-based solvents, etc., but 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 addition to the water-insoluble solvent.
  • examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone 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.
  • the catalyst used in the reaction is an acidic catalyst and is not particularly limited, but examples include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid and the like.
  • the amount of acid catalyst used is generally 0.1 to 10% by weight, preferably 1 to 5% by weight, relative to the aromatic amine resin.
  • the aromatic amine resin represented by the formula (3) is dissolved in toluene and N-methyl-2-pyrrolidone, maleic anhydride is added to generate amic acid, and then p-toluenesulfone is dissolved. An acid is added and the reaction is carried out while removing the water generated from the system under reflux conditions.
  • maleic anhydride is dissolved in toluene, and an N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the formula (3) is added under stirring to generate an amic acid, and then p- Toluenesulfonic acid is added, and the reaction is carried out while removing water generated from the system under reflux conditions.
  • maleic anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and an N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the formula (3) is added dropwise under stirring and reflux conditions. Meanwhile, the water azeotroped during the reaction is removed from the system, and toluene is returned to the system during the reaction (the above is the first-stage reaction).
  • the amount of maleic anhydride is usually 1.0 to 3.0 equivalents, preferably 1.2 to 2.0 equivalents, relative to the amino group of the aromatic amine resin represented by formula (3). Use 0 eq.
  • water is added to the reaction solution after the maleimidation reaction listed above to separate the resin solution layer and the aqueous layer, and excess maleic acid, maleic anhydride, aprotic polar Solvents, catalysts, etc. are dissolved in the aqueous layer, so they are separated and removed, and the same operation is repeated to thoroughly remove excess maleic acid, maleic anhydride, aprotic polar solvents, and catalysts. .
  • the time for the re-dehydration ring-closure reaction is usually 1 to 5 hours, preferably 1 to 3 hours, and if necessary, the aprotic polar solvent described above may be added.
  • the mixture is cooled and washed with water repeatedly until the washing water becomes neutral. Thereafter, after removing water by azeotropic dehydration under heating and reduced pressure, the solvent may be distilled off, another solvent may be added to adjust the resin solution to a desired concentration, or the solvent may be completely distilled. It may be removed and taken out as a solid resin.
  • Component (B) is not particularly limited as long as it has an unsaturated double bond and a polyphenylene ether structure.
  • unsaturated double bonds in component (B) include (meth)acrylic groups, styrene groups, allyl groups, vinyl groups and methallyl groups, with (meth)acrylic groups being preferred.
  • Commercially available products include SA-9000-111 (manufactured by Sabic, polyphenylene ether compound having a methacrylic group) represented by the following formula (2) and OPE-2St 1200 (Mitsubishi Gas Chemical Co., Ltd.) represented by the following formula (4).
  • Polyphenylene ether compound having a styrene group and the like.
  • compounds represented by the following formula (2) are preferable.
  • n is the number of repetitions, and the average value is 1 ⁇ n ⁇ 10)
  • n is the number of repetitions, and the average value is 1 ⁇ n ⁇ 10)
  • the weight average molecular weight (Mw) of component (B) is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, even more preferably from 2,000 to 4,000.
  • Mw weight average molecular weight
  • the weight average molecular weight can be measured using gel permeation chromatography or the like.
  • Component (B) can impart radical polymerizability by reacting a polyphenylene ether compound with a compound having an unsaturated double bond such as methacryl chloride, acryl chloride, or chloromethylstyrene.
  • 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 weight average molecular weight of 10,000 to 30,000.
  • a redistribution reaction for example, a high molecular weight polyphenylene ether compound is heated 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 such a redistribution reaction has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain, so that it is possible to maintain higher heat resistance.
  • 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 etc. in the case of the polyphenylene ether compound obtained by the polymerization reaction. Moreover, in the case of the polyphenylene ether compound obtained by the redistribution reaction, the molecular weight 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 component polyphenylene ether compound.
  • polyphenylene ether compounds include poly(2,6-dimethyl-1,4-phenylene ether). That is, in the case of the component (B) obtained by the redistribution reaction, a polyphenylene ether compound obtained by using poly(2,6-dimethyl-1,4-phenylene ether) as the high-molecular-weight polyphenylene ether compound. mentioned.
  • 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 weight ratio of component (A) and component (B) in the curable resin composition of the present invention is preferably 50/50 to 5/95, more preferably 30/70 to 5/95, and further It is preferably 25/75 to 5/95, particularly preferably 25/75 to 10/90.
  • the functional group equivalent ratio of component (A) and component (B) is preferably 0.2 to 4.2 equivalents of component (B) with respect to 1 equivalent of component (A), more preferably , 0.5 to 4.2 equivalents, more preferably 0.7 to 4.2 equivalents, and particularly preferably 0.7 to 2.0 equivalents.
  • component (B) If the amount of component (B) is less than 0.2 equivalents, the maleimide groups increase, resulting in deterioration of water absorption properties and brittleness of the cured product, resulting in a decrease in copper foil peel strength. On the other hand, when the component (B) is more than 4.2 equivalents, the crosslink density is lowered and the heat resistance is deteriorated.
  • any known resin material can be used in the curable resin composition of the present invention in addition to components (A) and (B).
  • resin material can be used in addition to components (A) and (B).
  • 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.
  • a maleimide compound other than component (A) may be used in combination.
  • Phenolic resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins may be exemplified below, but are limited to these. not to be
  • 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, 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 alcohol-substituted or unsubstituted acrylates (acrylate, methacrylate, etc.) polycondensates, maleimide
  • 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, '-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 in which
  • 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 resin may be zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead, etc., in order to trimerize the cyanate group to form a sym-triazine ring, if necessary. Catalysts such as 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, can be used as a curing agent for a curable 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 include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butylperoxyisopropyl).
  • -dialkyl peroxides such as benzene, peroxyketals such as t-butyl peroxybenzoate, 1,1-di-t-butylperoxycyclohexane, ⁇ -cumyl peroxyneodecanoate, t-butyl peroxy Neodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy Oxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxybenzoate, etc.
  • alkyl peresters di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butylperoxycarbonyl oxy)hexane and other peroxycarbonates, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide and other organic peroxides and azobisisobutyronitrile, 4,4 '-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) known curing accelerators of azo compounds such as, but not particularly limited to these do not have.
  • Ketone peroxides diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates and the like are preferred, and dialkyl peroxides are more preferred.
  • 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 large, the dielectric properties of the cured product deteriorate.
  • a curing accelerator other than a radical polymerization initiator may be added or used in combination with the curable resin composition of the present invention, if necessary.
  • 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
  • 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 myristate) and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate, etc.);
  • a blending amount of the curing accelerator is, if necessary, 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the curable resin composition.
  • the curable resin composition of the present invention can contain a phosphorus-containing compound as a flame retardancy-imparting component.
  • 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, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylenebis(dixylene phosphate), 1,4-phenylene bis (dixylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate) and other phosphoric acid esters; 9,10-dihydro-9-oxa-10-phospha Phosphanes such as phenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phospha
  • phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixylenylphosphate), 1,4-phenylenebis( dixylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
  • the content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound)/resin component in the curable resin composition (weight ratio) of 0.1 to 0.6. 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.
  • 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-te
  • 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. It is 0.05 to 20 parts by mass.
  • 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 that are spherical or crushed from these powders. be able to.
  • 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.
  • additives can be added to the curable resin composition of the present invention 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 blended is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less per 100 parts by mass of the resin component.
  • 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, high adhesiveness, low dielectric constant and low dielectric loss tangent. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, high adhesiveness, low dielectric constant and low dielectric loss tangent. 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 for preparing the curable resin composition of the present invention is not particularly limited, it is prepared by dispersing or dissolving each component in a solvent or the like as described above, uniformly mixing, and optionally distilling off the solvent. Alternatively, it may be prepolymerized.
  • component (A) and component (B) are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent.
  • curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate ester compounds, phenol resins, acid anhydride compounds, and other additives are added to prepolymers. may be changed.
  • 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.
  • a uniform curable resin composition is obtained by kneading using a device such as a kneader, roll, planetary mixer, etc. at a temperature within the range of 50 to 100 ° C. do.
  • a device such as a kneader, roll, planetary mixer, etc.
  • After pulverizing the obtained curable resin composition it is molded into a cylindrical tablet by a molding machine such as a tablet machine, or it is made into a granular powder or a powdery molding, or these compositions are used as a surface support. It is also possible to form a curable resin composition molded article by melting it on a surface and molding it into a sheet having a thickness of 0.05 mm to 10 mm.
  • the obtained molded article becomes a non-sticky molded article at 0 to 20°C, and its fluidity and curability hardly deteriorate even when stored at -25 to 0°C for 1 week or longer.
  • 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. If the amount of solvent is less than this range, the viscosity of the varnish will increase and the workability will be deteriorated. 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.
  • a sheet-like adhesive is obtained.
  • 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 (gel permeation chromatography) analysis Manufacturer Waters Column: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 0.5 ml/min. Column temperature: 40°C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refraction detector)
  • ⁇ DSC analysis Manufacturer TA Instruments Equipment: DSC2500 Heating rate: 10°C/min Measurement temperature range: 30°C to 350°C
  • ⁇ DMA Manufacturer TA Instruments Device: DMAQ800 Measurement mode: Tensile Heating rate: 2°C/min. Measurement temperature range: 25°C to 350°C Measurement frequency: 10Hz The temperature at which the value of tan ⁇ was maximum was defined as Tg.
  • ⁇ Td5 analysis Manufacturer Seiko Instruments Inc. Device: TG/DTA6200 Measurement temperature range: 30°C to 580°C Heating rate: 10°C/min
  • ⁇ TMAs Manufacturer TA Instruments Device: TMAQ400 Measurement mode: Tensile Heating rate: 2°C/min. Measurement temperature range: 25°C to 330°C
  • ⁇ Peel strength test Manufacturer Shimadzu Corporation Equipment: Autograph AGS-X Peel test tensile speed: 50mm/min Rough surface of 18 ⁇ m thick electrolytic copper foil (CF-T4X-SV-18: manufactured by Fukuda Metal Foil & Powder Co., Ltd.) and 35 ⁇ m thick electrolytic copper foil (CF-T9B-HTE: manufactured by Fukuda Metal Foil & Powder Co., Ltd. ), and cured at a pressure of 1 MPa at 220° C. for 2 hours to prepare a test piece. After cutting the obtained test piece into a width of 2 cm, the electrodeposited copper foil having a thickness of 18 ⁇ m was cut so as to leave a width of 1 cm and removed. An electrodeposited copper foil having a width of 1 cm and a thickness of 18 ⁇ m was pulled in a 90° direction at the above test speed to measure the peel strength.
  • test piece having a width of 2.5 mm and a length of 5 cm was dried in a dryer at 120°C for 2 hours, and then measured. Furthermore, after the test piece was immersed in water for 24 hours, it was taken out and allowed to stand in an environment of 25°C and 30% for 24 hours, and then the measurement was performed again.
  • the separated lower aqueous layer was removed, and the reaction solution was washed with water repeatedly until the washing solution became neutral. Then, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure using a rotary evaporator to obtain 158 parts of the aromatic amine resin (A-1) represented by the formula (2).
  • the aromatic amine resin (A-1) had an amine equivalent of 186.1 g/eq and a softening point of 58.8°C.
  • a GPC chart is shown in FIG.
  • the softening point was 115.5° C. and the viscosity was 6.0 Pa ⁇ s.
  • a GPC chart is shown in FIG.
  • Examples 1 to 5 A maleimide compound and a polyphenylene ether compound having an unsaturated double bond are weighed out at the ratio shown in Table 1, and toluene is added so that the resin solid content becomes 50%. made. The solubility and compatibility of the resin at this time were visually confirmed and evaluated under the conditions described later. The results are shown in Table 1. Further, DCP (dicumyl peroxide, manufactured by Kayaku Nourion Co., Ltd.) was dissolved in the varnish as a curing accelerator. A curable resin composition was prepared by heating the varnish in which the curing accelerator was dissolved in a vacuum dryer at 80° C. for 30 minutes and at 120° C. for 1 hour.
  • the resulting curable resin composition was sandwiched between copper foils and cured at 220° C. for 2 hours under vacuum with a pressure of 1 MPa. The curability at this time was confirmed and evaluated under the conditions described later. Table 1 shows the results of various measurements on the obtained cured product.
  • Solubility criteria ⁇ No precipitate in solution ⁇ There is precipitate in solution Compatibility criteria: ⁇ Compatible ⁇ Not compatible (phase separation is doing) 220 ° C. Curability Judgment Conditions: ⁇ : A cured product can be obtained: ⁇ : A cured product cannot be obtained (the cured product is brittle and cannot be taken out)
  • Examples 1 to 5 have good solvent solubility and compatibility, the curing reaction proceeds well at 220° C. for 2 hours, and it is confirmed that they have excellent heat resistance, copper foil peel strength, moisture resistance, and dielectric properties. was done. Since Comparative Example 1 used a large amount of the maleimide compound (M-1), it was confirmed that the water absorption rate and dielectric properties were high (bad). When the maleimide compound (M-1) is used alone as in Comparative Example 2, the heat resistance and dielectric loss tangent are good, but the copper foil peel strength is low and the water absorption rate is high, so the dielectric loss tangent after water absorption deteriorates. was confirmed.
  • a single polyphenylene ether compound having an unsaturated double bond as in Comparative Example 3 did not cure under the curing conditions of 220° C. for 2 hours.
  • solvent solubility and compatibility were poor, resulting in high (poor) dielectric properties and dielectric properties after water absorption.

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WO2021149733A1 (ja) * 2020-01-24 2021-07-29 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、プリプレグ及びプリント配線板

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