Maleimide resin, curable resin composition and cured product thereof

Abstract

The object of the present invention is to provide a maleimide resin having a specific structure, a curable resin composition and a cured product thereof which can be preferably used for sealing or circuit substrates of electrical and electronic parts, carbon fiber composites, etc. and have high heat resistance and excellent low dielectric properties. A maleimide resin represented by the following formula (1). In formula (1), R represents a hydrocarbon group having 1 to 18 carbon atoms. m represents an integer of 1 to 4, n represents an average value, and 1≦n≦20. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a novel maleimide resin and a curable resin composition thereof and a cured product thereof, which can be preferably used in electrical and electronic parts such as semiconductor sealing materials, printed wiring boards, and build-up laminates, or lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics. Background Art

[0002] In recent years, laminated boards equipped with electrical and electronic components have been required to have a wide range of characteristics and be more sophisticated due to the expansion of their application areas. The mainstream of existing semiconductor chips is mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs (central processing units)) are mostly mounted on laminated boards made of polymer materials.

[0003] In particular, in semiconductor packages (hereinafter referred to as PKG) used in smart phones, in order to meet the requirements of miniaturization, thinning and high density, the PKG substrate is required to be thinner, but if the PKG substrate is thinner, the rigidity will decrease, so the heating when the PKG is soldered and mounted on the motherboard (printed circuit board (PCB)) will cause large warping and other undesirable conditions. In order to reduce the above-mentioned problems, a PKG substrate material with a high Tg above the soldering mounting temperature is required.

[0004] In addition, the fifth-generation communication system "5G", which is currently being developed at an accelerated pace, is expected to further promote large-capacity and high-speed communication. The demand for low dielectric loss tangent materials is increasing, and it is required to have both heat resistance and dielectric properties in areas where epoxy resin cannot cope.

[0005] Furthermore, in the automotive field, electronicization is advancing, and sometimes precision electronic equipment is installed near the engine drive unit, which requires a higher level of heat and humidity resistance. SiC semiconductors are beginning to be used in electric vehicles and air conditioners, and the sealing materials for semiconductor elements require extremely high heat resistance, so existing epoxy resin sealing materials are no longer able to cope with it.

[0006] In this context, research is underway on polymer materials that have both heat resistance and low dielectric loss tangent properties. For example, Patent Document 1 proposes a composition comprising a maleimide resin and a phenolic resin containing an acrylic group. However, on the other hand, since the phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, it cannot be said that the electrical properties are sufficient. In addition, Patent Document 2 discloses an allyl ether resin that uses allyl groups to replace hydroxyl groups. However, it is shown that Claisen Rearrangement occurs at 190°C, and at a general substrate molding temperature of 200°C, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so the electrical properties cannot be satisfied.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Laid-Open No. 04-359911

[0010] Patent Document 2: International Publication No. 2016 / 002704 Summary of the invention

[0011] Problems to be solved by the invention

[0012] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable resin, a curable resin composition and a cured product thereof which exhibit excellent heat resistance and electrical properties and have good curability.

[0013] Technical means of solving problems

[0014] The present inventors have conducted intensive studies to solve the above problems and have found that a cured product of a curable resin composition using a novel maleimide resin has excellent heat resistance and low dielectric properties, thereby completing the present invention.

[0015] That is, the present invention relates to the following [1] to [6]. [1]

[0017] A maleimide resin represented by the following formula (1).

[0018] [Chemistry 1]

[0019]

[0020] (In formula (1), R represents a hydrocarbon group having 1 to 18 carbon atoms. m represents an integer of 1 to 4, n represents an average value, and 1≦n≦20). [2]

[0022] The maleimide resin according to the aforementioned item [1] is obtained by reacting an aromatic amine resin represented by the following formula (2) with maleic acid or maleic anhydride.

[0023] [Chemistry 2]

[0024]

[0025] (In formula (2), R represents a hydrocarbon group having 1 to 18 carbon atoms. m represents an integer of 1 to 4, and n represents an average value, and 1≦n≦20). [3]

[0027] The maleimide resin according to the above item [1] or [2], wherein R in the formula (1) is a methyl group. [4]

[0029] The maleimide resin according to any one of the above items [1] to [3], which is represented by the following formula (3).

[0030] [Chemistry 3]

[0031]

[0032] (where n represents the average value, and 1≦n≦20). [5]

[0034] A curable resin composition comprising the maleimide resin according to any one of the above items [1] to [4]. [6]

[0036] A cured product obtained by curing the curable resin composition according to the above item [5].

[0037] Effects of the Invention

[0038] The cured product of the curable resin composition containing the maleimide resin of the present invention exhibits high heat resistance and low dielectric properties. Therefore, the curable resin composition of the present invention is useful for sealing of electric and electronic parts, circuit boards, carbon fiber composites, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a 1H-nuclear magnetic resonance (NMR) chart of Synthesis Example 1 of the present invention.

[0040] Figure 2 This is a 1H-NMR chart of Example 1 of the present invention. DETAILED DESCRIPTION

[0041] Hereinafter, the maleimide resin of the present invention will be described in detail.

[0042] The maleimide resin of the present invention is represented by the following formula (1).

[0043] [Chemistry 4]

[0044]

[0045] (In formula (1), R represents a hydrocarbon group having 1 to 18 carbon atoms. m represents an integer of 1 to 4, n represents an average value, and 1≦n≦20).

[0046] In the above formula (1), R is preferably a hydrocarbon group having 1 to 3 carbon atoms, and m is preferably 1 or 2. n is preferably 1≦n≦10, and more preferably 1≦n≦5.

[0047] The maleimide resin of the present invention is particularly preferably represented by the following formula (3).

[0048] [Chemistry 5]

[0049]

[0050] (In formula (3), n represents the average value, and 1≦n≦20).

[0051] In the formula (3), n is preferably 1≦n≦10, and more preferably 1≦n≦5.

[0052] The maleimide resin of the present invention is obtained by reacting an aromatic amine resin represented by the following formula (2) with maleic acid or maleic anhydride.

[0053] [Chemistry 6]

[0054]

[0055] (In formula (2), R represents a hydrocarbon group having 1 to 18 carbon atoms. m represents an integer of 1 to 4, and n represents an average value, and 1≦n≦20).

[0056] The maleimide resin of the present invention is particularly preferably represented by the following formula (4).

[0057] [Chemistry 7]

[0058]

[0059] (where n represents the average value, and 1≦n≦20).

[0060] The preferred ranges of R, m, and n in formula (2) and formula (4) are the same as those in formula (1).

[0061] The method for preparing the compound of formula (2) or formula (4) is not particularly limited. For example, aniline and alkylbenzene formalin resin can be reacted under an acid catalyst such as hydrochloric acid or activated clay, or aniline, formaldehyde and alkylbenzenes can be reacted under an acid catalyst such as hydrochloric acid or activated clay. In the case of using hydrochloric acid as a catalyst, neutralization is performed using an alkali metal such as sodium hydroxide or potassium hydroxide, extraction is performed using an aromatic hydrocarbon solvent such as toluene or xylene, and then washing with water until the drainage becomes neutral, and the solvent is distilled off using an evaporator, etc., thereby obtaining the target aromatic amine resin.

[0062] Examples of the alkylbenzaldehyde resins used include, but are not limited to, toluene aldehyde resins, o-xylene aldehyde resins, m-xylene aldehyde resins, p-xylene aldehyde resins, 1,2,3-trimethylbenzaldehyde resins, 1,2,4-trimethylbenzaldehyde resins, 1,2,5-trimethylbenzaldehyde resins, 1,3,5-trimethylbenzaldehyde resins, 1,2,3,4-tetramethylbenzaldehyde resins, 1,2,3,5-tetramethylbenzaldehyde resins, 1,2,4,5-tetramethylbenzaldehyde resins, 1,3,5-triethylbenzaldehyde resins, 1,3,5-tripropylbenzaldehyde resins, 1,3,5-triisopropylbenzaldehyde resins, 1,3,5-tributylbenzaldehyde resins, and 1,3,5-tri-tert-butylbenzaldehyde resins. These may be used alone or in combination of two or more. From the viewpoint of dielectric properties and heat resistance, it is preferably substituted by a hydrocarbon group having 1 to 5 carbon atoms, more preferably substituted by a hydrocarbon group having 1 to 3 carbon atoms, and further preferably substituted by a methyl group. As the carbon number of the hydrocarbon group increases, the rigidity of the molecule is difficult to ensure, and the molecule is prone to vibration, which becomes a cause of reducing dielectric properties or heat resistance. The amount of the alkylbenzaldehyde resin used is usually 0.05% to 0.8% by weight, preferably 0.1% to 0.6% by weight, relative to 1% by weight of the aniline used.

[0063] During the reaction, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, solid acids such as activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins may be used as needed. These may be used alone or in combination of two or more. From the perspective of simplicity and economy of the manufacturing process, it is preferred to use a solid acid that can be reused (activated clay, acid clay, white carbon, zeolite, solid acids such as silica alumina, and acidic ion exchange resins). The amount of the catalyst used is generally 0.1 to 0.8 moles, preferably 0.2 to 0.7 moles, relative to 1 mole of the aniline used. If it is too much, the viscosity of the reaction solution is too high and stirring may become difficult. If it is too little, the reaction may be slow (for the case of using the reusable solid acid catalyst, it is 1% to 50% by weight, preferably 5% to 40% by weight, and more preferably 10% to 30% by weight relative to the amount of aniline loaded. When the amount of solid acid used is more than the above range, it is difficult to ensure the fluidity of the reaction solution. When the amount of solid acid used is less than the above range, the reaction will not proceed fully, or the reaction time will be longer). The reaction can be carried out using organic solvents such as toluene and xylene as needed, or it can be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of aniline, an alkylbenzaldehyde resin and a solvent, when the catalyst contains water, water is removed from the system by azeotropy. Then, the reaction is carried out at 40°C to 180°C, preferably 50°C to 170°C for 0.5 hours to 20 hours. Thereafter, the temperature is raised while removing water or low molecular weight components generated in the system by azeotropic dehydration, and the reaction is carried out at 180° C. to 300° C., preferably 190° C. to 250° C., more preferably 200° C. to 240° C. for 5 to 50 hours, preferably 5 to 20 hours. After the reaction is completed, the acidic catalyst is neutralized with an alkaline aqueous solution, and a water-insoluble organic solvent is added to the oil layer, and water washing is repeated until the waste water becomes neutral (when the reusable solid acid catalyst is used, the catalyst is removed by filtration).

[0064] The softening point of the aromatic amine resin is preferably 80° C. or less, more preferably 70° C. or less. If the softening point is higher than 80° C., the viscosity of the maleimide resin becomes high, making it difficult to impregnate the carbon fiber or glass fiber. When the diluent solvent is added to reduce the viscosity, the resin may not be sufficiently attached to the fibrous material during the impregnation step.

[0065] The maleimide resin of the present invention is obtained by reacting maleic acid or maleic anhydride with an aromatic amine resin of formula (2) or (4) in the presence of a solvent and a catalyst, for example, by using the method described in Japanese Patent Gazette No. 6429862. In the above case, it is necessary to remove the water generated in the reaction from the system, so the solvent used in the reaction uses a water-insoluble solvent. For example, 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 solvents such as methyl isobutyl ketone and cyclopentanone, etc., but are not limited to these, and two or more thereof may be used in combination. In addition, in addition to the water-insoluble solvent, a non-protonic polar solvent may also be used in combination. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. may be mentioned, and two or more thereof may be used in combination. When an aprotic polar solvent is used, it is preferred to use an aprotic polar solvent having a higher boiling point than the non-water-soluble solvent used in combination. The catalyst is not particularly limited, and acidic catalysts such as p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, etc. can be cited. For example, maleic acid is dissolved in toluene, and an N-methylpyrrolidone solution of the aromatic amine resin of the present invention is added under stirring, and p-toluenesulfonic acid is added thereto, and the reaction is carried out while removing the generated water from the system under reflux conditions.

[0066] The curable resin composition of the present invention may also use any existing material as the curable resin other than the maleimide resin of the present invention. Specifically, phenol resin, epoxy resin, amine resin, active olefin resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, acrylic resin, methacrylic resin, active ester resin, etc. are listed. In terms of the balance of heat resistance, adhesion, and dielectric properties, it is preferred to contain epoxy resin, active olefin resin, and cyanate resin. By containing these curable resins, the brittleness of the cured product can be improved and the adhesion to the metal can be improved, and the cracks of the package in the reliability test such as solder reflow or hot and cold cycle can be suppressed. The curable resin other than the maleimide resin of the present invention can be used alone or in combination.

[0067] The amount of the curable resin used is generally less than 10 times by mass, preferably less than 3 times by mass, more preferably less than 2 times by mass, and particularly preferably less than 1.5 parts by mass relative to the maleimide resin of the present invention. In the case of more than 10 times by mass, the concentration of the maleimide resin of the present invention becomes low, and sufficient heat resistance or dielectric properties may not be obtained. In addition, the preferred lower limit is 0.2 times by mass or more, and more preferably 0.5 times by mass or more.

[0068] Phenolic resins: polycondensates of 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, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.); polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, dicyclopentadiene, terpenes, dicyclopentadiene ... Polymers of phenols (vinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc.); polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); phenol resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.); polycondensates of bisphenols and various aldehydes; polyphenylene ethers.

[0069] Epoxy resin: the above-mentioned phenol resin; glycidyl ether epoxy resin obtained by glycidylating alcohols; alicyclic epoxy resin represented by 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate; glycidylamine epoxy resin represented by tetraglycidyl diaminodiphenylmethane (TGDDM) or triglycidyl-p-aminophenol; glycidyl ester epoxy resin.

[0070] Amine resin: diaminodiphenylmethane; diaminodiphenyl sulfone; isophoronediamine; naphthalene diamine; aniline novolac; o-ethylaniline novolac; aniline resin obtained by the reaction of aniline with xylylene chloride; amine resin obtained by the reaction of aniline described in Japanese Patent No. 6429862 with substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.).

[0071] Resins containing active olefins: polycondensates of the above phenolic resins and halogen compounds containing active olefins (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, etc.); polycondensates of phenols containing active olefins (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 of epoxy resins or alcohols and substituted or unsubstituted Condensation products of substituted acrylates (acrylates, methacrylates, etc.); maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis〔4-(4-maleimidephenoxy)phenyl〕propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene).

[0072] Isocyanate resin: aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc.; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, etc.; polyisocyanates such as biuret forms of one or more isocyanate monomers or isocyanate forms obtained by trimerizing the diisocyanate compounds; polyisocyanates obtained by urethanization reaction of the isocyanate compounds with polyol compounds.

[0073] Polyamide resin: selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanealactam, ω-laurolactam) and 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, etc.); cyclopentanediamine alicyclic diamines such as hexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylene diamine; and a mixture of dicarboxylic acids (aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids) as main raw materials.

[0074] Polyimide resin: the diamine and tetracarboxylic acid dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylene-4,4'-diphthalic acid dianhydride, 2,2'-propylene-4,4 '-Diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic dianhydride, 1,4-bis[ 2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, 2,3,6, 7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride) polycondensate.

[0075] Cyanate resin: a cyanate compound obtained by reacting a phenol resin with a cyanogen halide, and specific examples thereof include dicyanatobenzene, tricyanatobenzene, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl)sulfide, phenol novolac cyanate, and a cyanate compound obtained by converting a hydroxyl group of a phenol-dicyclopentadiene co-condensate into a cyanate group, but the present invention is not limited thereto.

[0076] In addition, the cyanate compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferred as the cyanate compound because of its low hygroscopicity, flame retardancy, and excellent dielectric properties.

[0077] The cyanate resin may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, or dibutyltin maleate in order to trimerize the cyanate group to form a s-triazine ring as necessary.

[0078] Active ester compound: A compound having one or more active ester groups in one molecule can be used as a hardener for curable resins other than the essential components described in the present invention such as epoxy resins as required. As active ester hardeners, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are preferred. The active ester hardener is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound with at least one of a hydroxyl compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester hardener obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound is preferred.

[0079] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0080] Examples of the phenol compound or naphthol compound 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, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, pyroglucinol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

[0081] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" means a divalent structural unit containing phenylene-dicyclopentylene-phenylene.

[0082] Examples of commercially available active ester hardeners include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC Corporation), which are active ester compounds containing a naphthalene structure. ; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener for an acetylated product of phenol novolac; "EXB-9050L-62M" manufactured by DIC Corporation as an active ester hardener containing a phosphorus atom, etc.

[0083] In the curable resin composition of the present invention, in order to promote the self-polymerization of the curable resin capable of free radical polymerization such as maleimide resin or the free radical polymerization with other components, it is preferable to use a free radical polymerization initiator. Examples of the free radical polymerization initiator that can be used include: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxyketals such as tert-butyl peroxybenzoate and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethylbutyl peroxy Alkyl peroxy acid esters such as hexanoate, tert-butyl peroxy-3,5,5-trimethyl hexanoate, and tert-amyl peroxybenzoate; peroxy carbonates such as di-2-ethylhexyl peroxy dicarbonate, bis (4-tert-butyl cyclohexyl) peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate, and 1,6-bis (tert-butyl peroxy carbonyl oxy) hexane; organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy octanoate, and lauroyl peroxide, or azo compounds such as azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis (2,4-dimethylvaleronitrile) and the like, but are not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxy ketals, alkyl peroxy acid esters, and peroxy carbonates are preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is large, the molecular weight cannot be sufficiently increased during the polymerization reaction.

[0084] The curable resin composition of the present invention may contain a curing accelerator (curing catalyst) as needed. Specific examples of usable hardening accelerators include tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide; quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt is a halogen, an organic acid ion, a hydroxide ion, etc., and is not particularly limited, but is particularly preferably an organic acid ion or a hydroxide ion), transition metal compounds (transition metal salts) such as zinc compounds such as tin octanoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), or zinc phosphates (zinc octylphosphate, zinc stearylphosphate, etc.). The amount of the curing accelerator to be used may be 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, as required.

[0085] The curable resin composition of the present invention may also contain a phosphorus-containing compound as a flame retardancy imparting component. The phosphorus-containing compound may be a reactive phosphorus-containing compound or an additive phosphorus-containing compound. Specific examples of phosphorus-containing compounds include: trimethyl phosphate, triethyl phosphate, tritolyl phosphate, tri(xylyl) phosphate, tolyl diphenyl phosphate, tolyl-2,6-di(xylyl) phosphate, 1,3-phenylene bis(di(xylyl) phosphate), 1,4-phenylene bis(di(xylyl) phosphate), 4,4'-biphenyl(di(xylyl) phosphate) and other phosphates; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-( Phosphanes such as 2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with active hydrogen of the above-mentioned phosphanes, red phosphorus, etc., preferably phosphates, phosphanes or phosphorus-containing epoxy compounds, and particularly preferably 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4'-biphenyl(di(xylyl)phosphate) or phosphorus-containing epoxy compounds. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound) / (total epoxy resin) of 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, there is a risk of adversely affecting the hygroscopicity and dielectric properties of the cured product.

[0086] Furthermore, an antioxidant may be added to the curable resin composition of the present invention as needed. Examples of usable antioxidants include phenolic, sulfur, and phosphorus antioxidants. The antioxidant may be used alone or in combination of two or more. The amount of the antioxidant used is generally 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, relative to 100 parts by weight of the resin component in the curable resin composition of the present invention. These antioxidants may be used alone or in combination of two or more. In the present invention, phosphorus antioxidants are particularly preferred.

[0087] Specific examples of phenolic antioxidants include monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; and 2,2'-methylenebis(4 -methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 2,2- Bisphenols such as thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, and calcium bis(3,5-di-tert-butyl-4-hydroxybenzylsulfonate); 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5 -Trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid ethylene glycol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other high molecular weight phenols.

[0088] Specific examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

[0089] Specific examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butyl-4-methylphenyl)phosphite, Phosphites such as bis[2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl] halogenated phosphite; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

[0090] Furthermore, a light stabilizer may be added to the curable resin composition of the present invention as required. The light stabilizer is preferably a hindered amine light stabilizer, and particularly preferably a hindered amine light stabilizer (HALS). The HALS is not particularly limited, and typical HALS include: a polycondensate of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a polycondensate of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidyl succinate, and poly{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2 HALS may be used alone or in combination of two or more.

[0091] Furthermore, in the curable resin composition of the present invention, a binder resin may also be formulated as needed. As binder resins, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (nitrile butadiene rubber, NBR) -phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins, etc. can be cited, but are not limited to these. The amount of binder resin formulated is preferably within a range that does not damage the flame retardancy and heat resistance of the cured product. Relative to 100 parts by mass of the resin component, 0.05 to 50 parts by mass is usually used as needed, preferably 0.05 to 20 parts by mass.

[0092] Furthermore, in the curable resin composition of the present invention, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, glass powder and other powders, or inorganic fillers in the form of spheres or crushed forms thereof can be added as needed. In addition, in particular, when a curable resin composition for semiconductor encapsulation is obtained, the amount of the inorganic filler used in the curable resin composition is usually in the range of 80% to 92% by mass, preferably in the range of 83% to 90% by mass.

[0093] In the curable resin composition of the present invention, existing additives may be formulated as needed. Specific examples of usable additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine green and other colorants. The amount of these additives formulated is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, relative to 100 parts by mass of the curable resin composition.

[0094] The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at a predetermined ratio, and generally pre-curing at 130° C. to 180° C. for 30 seconds to 500 seconds, and then post-curing at 150° C. to 200° C. for 2 hours to 15 hours, thereby allowing a sufficient curing reaction to obtain a cured product of the present invention. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and then cured after removing the solvent.

[0095] The curable resin composition of the present invention obtained in the above manner has moisture resistance, heat resistance, and high adhesion. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, and high adhesion. Specifically, it is useful as a material for all electrical and electronic parts such as insulating materials, laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), sealing materials, and resists. In addition, in addition to molding materials and composite materials, it can also be used in the fields of coating materials, adhesives, etc. In particular, in semiconductor sealing, resistance to solder reflow is beneficial.

[0096] The semiconductor device is sealed with the curable resin composition of the present invention. Examples of the semiconductor device include dual in-line package (DIP), quad flat package (QFP), ball grid array (BGA), chip size package (CSP), small outline package (SOP), thin small outline package (TSOP), and thin quad flat package (TQFP).

[0097] The preparation method of the curable resin composition of the present invention is not particularly limited, and the components may be simply mixed uniformly, or prepolymerized. For example, the curable resin of the present invention may be heated in the presence or absence of a catalyst, in the presence or absence of a solvent, thereby prepolymerizing. Similarly, in addition to the curable resin of the present invention, curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenol resins, acid anhydride compounds, and other additives may be added to prepolymerize. For mixing or prepolymerizing the components, for example, an extruder, a kneader, a roller, etc. are used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.

[0098] As a method of uniform mixing, the resin composition can be uniformly mixed by mixing at a temperature in the range of 50°C to 100°C using a kneader, a roller, a planetary mixer or the like. The obtained resin composition can be crushed and then molded into a cylindrical ingot using a molding machine such as a tablet machine, or into a granular powder or a powdery molded body, or the composition can be melted on a surface support and molded into a sheet with a thickness of 0.05mm to 10mm to form a curable resin composition molded body. The obtained molded body is a non-sticky molded body at 0°C to 20°C, and the fluidity and curability are hardly reduced even if stored at -25°C to 0°C for more than 1 week.

[0099] The obtained molded body can be molded into a cured product using a transfer molding machine or a compression molding machine.

[0100] An organic solvent may be added to the curable resin composition of the present invention to prepare a varnish-like composition (hereinafter referred to as varnish). The curable resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to prepare a varnish as needed, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heated and dried, and the obtained prepreg is hot-pressed to prepare a cured product of the curable resin composition of the present invention. The solvent used in this case is usually 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. In addition, if it is a liquid composition, a cured product of a curable resin containing carbon fibers may be obtained directly, for example, by resin transfer molding (RTM).

[0101] In addition, 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 the flexibility of the B-stage. Such a film-type resin composition is obtained by preparing the curable resin composition of the present invention into the curable resin composition varnish and applying it on a release film, removing the solvent under heating, and then performing B-stage, thereby obtaining a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate, etc.

[0102] The curable resin composition of the present invention can be heated and melted, reduced in viscosity, and impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. 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, and further inorganic fibers other than glass or polyparaphenyleneterephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers, but are not particularly limited to these. The shape of the substrate is not particularly limited, and for example, woven fabrics, non-woven fabrics, rovings, chopped strand mats, etc. can be listed. In addition, as the weaving method of the woven fabric, there are known plain weave, basket weave, twill weave, etc., which can be appropriately selected from these existing weaving methods according to the target use or performance. In addition, it is preferred to use a glass woven fabric that has been subjected to fiber opening treatment or surface treatment using a silane coupling agent or the like. The thickness of the substrate is not particularly limited, and is preferably about 0.01 mm to 0.4 mm. In addition, a prepreg can also be obtained by impregnating the varnish in the reinforcing fiber and heating and drying it.

[0103] The laminate of the present embodiment includes more than one prepreg. The laminate is not particularly limited as long as it is a laminate including more than one prepreg, and may also have any other layer. As a manufacturing method of the laminate, a generally existing method can be appropriately applied without particular limitation. For example, when forming a laminate with a metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used, and a laminate can be obtained by stacking the prepregs on each other and performing heating and pressurizing. At this time, the heating temperature is not particularly limited, preferably 65°C to 300°C, and more preferably 120°C to 270°C. In addition, the pressure of the pressurization is not particularly limited. If the pressure is too large, the solid content of the resin of the laminate is difficult to adjust, and the quality is unstable. In addition, if the pressure is too small, the air bubbles or the adhesion between the layers deteriorate, so it is preferably 2.0MPa to 5.0MPa, and more preferably 2.5MPa to 4.0MPa. The laminated plate of the present embodiment includes a layer having a metal foil, and can be preferably used as a metal foil clad laminated plate described later.

[0104] The prepreg is cut into a desired shape, and after being laminated with copper foil or the like as needed, the curable resin composition is heated and cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like, thereby obtaining an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0105] The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and coatings. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, and can therefore be preferably used in sealing materials for semiconductor elements, sealing materials for liquid crystal display elements, sealing materials for organic electroluminescence (EL) elements, printed wiring boards, build-up laminates and other electrical and electronic parts, or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

[0106] Example

[0107] Next, the present invention will be described in more detail by way of examples. Hereinafter, parts are parts by weight unless otherwise specified. In addition, the present invention is not limited to these examples.

[0108] Various analytical methods used in the Examples are described below.

[0109] <Amine equivalent>

[0110] The obtained value was defined as the amine equivalent in accordance with Japanese Industrial Standards (JIS) K-7236 Annex A (corrected method for glycidylamine).

[0111] <Softening point>

[0112] The measurement was conducted in accordance with JIS K-7234.

[0113] <ICI viscosity (150℃)>

[0114] The measurement was conducted in accordance with JIS K-7117-2.

[0115] <Weight average molecular weight (Mw)>

[0116] Calculation was performed using polystyrene conversion using a polystyrene standard solution.

[0117] Gel permeation chromatograph (GPC): DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0118] Column: Shodex KF-603, KF-602×2, KF-601×2

[0119] Linking eluent: tetrahydrofuran

[0120] Flow rate: 0.5ml / min.

[0121] Column temperature: 40℃

[0122] Detector: RI (refractive index) (differential refractometer)

[0123] [Synthesis example 1]

[0124] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, 210 parts of xylene formaldehyde resin (NIKANOL G, manufactured by Fudow Co., Ltd.), 738 parts of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 parts of toluene, and 95 parts of activated clay were placed, and reacted at 120°C for 1 hour, and then the temperature was raised to 150°C while the distillate was extracted and maintained for 4 hours. Thereafter, the temperature was raised to 200°C, and the reaction was carried out at 200°C for 10 hours. After cooling, the mixture was diluted with 300 parts of toluene, and activated clay (manufactured by Japan Activated Clay Co., Ltd.) was removed by filtration. The solvent and excess aniline were then distilled off under reduced pressure with heating to obtain 314 parts of aromatic amine resin (A1) (softening point: 66.6°C, melt viscosity: 0.23 Pa·s, amine equivalent: 198 g / eq, Mw: 734). Figure 1 This is a 1H-nuclear magnetic resonance (NMR) chart of Synthesis Example 1 of the present invention.

[0125] [Example 1]

[0126] In a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer, 186 parts of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 250 parts of toluene were placed, and the water and toluene heated to form an azeotropic mixture were cooled and separated, and only the toluene as the organic layer was returned to the system for dehydration. Next, 250 parts of the aromatic amine resin (A1) obtained in Synthesis Example 1 was dissolved in a mixed solvent of 250 parts of N-methyl-2-pyrrolidone and 250 parts of toluene to obtain a resin solution, and the obtained resin solution was added dropwise over 1 hour while the system was kept at 80°C to 85°C. After the addition was completed, the reaction was carried out at the same temperature for 2 hours, 5 parts of p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the condensed water and toluene formed by azeotropy were cooled and separated under reflux conditions, and only the toluene as the organic layer was returned to the system for dehydration, and the reaction was carried out for 20 hours. After the reaction, 3000 parts of toluene and 300 parts of N-methyl-2-pyrrolidone were added, and p-toluenesulfonic acid and excess maleic anhydride were removed by repeated water washing, and the water was removed from the system by azeotropy by heating. Then, the reaction solution was concentrated to obtain a resin solution containing 70% by weight of maleimide resin (M1). The weight average molecular weight (Mw) of M1 is 1204. The 1H-NMR diagram of the maleimide resin (M1') taken out in solid form by vacuum concentration is shown in Figure 2 middle.

[0127] 1H-NMR (400MHz, dimethylsulfoxide (DMSO)-d6): δ (ppm) 1.64-2.33 (m, 83H), 2.70 (s, 6H), 3.30 (t, 2H), 3.40-4.10 (m, 31H), 6.43-7.40 (m, 109H)

[0128] [Example 2, Comparative Example 1, Comparative Example 2]

[0129] The maleimide compound (M1) obtained in Example 1 and taken out in solid form by reduced pressure concentration (M1'), biphenyl aralkyl type maleimide resin (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.), biphenyl aralkyl type epoxy resin (NC-3000-L, manufactured by Nippon Kayaku Co., Ltd.), biphenyl aralkyl type phenol resin (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.), and 2E-4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.) as a curing accelerator were prepared in the proportions (parts by mass) shown in Table 1, heated and melted in a metal container, poured directly into a mold, and cured at 220°C for 2 hours.

[0130] <Heat resistance test>

[0131] Glass transition temperature: The temperature at which tan δ reaches a maximum value as measured by a dynamic viscoelasticity tester.

[0132] Dynamic viscoelasticity tester: DMA-2980 manufactured by TA-instruments

[0133] Heating rate: 2℃ / min

[0134] <Dielectric constant test and dielectric loss tangent test>

[0135] · The 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. was used for testing using the cavity resonator perturbation method. The sample size was 1.7 mm wide x 100 mm long and 1.7 mm thick.

[0136] [Table 1]

[0137]

[0138] M1': The maleimide resin obtained in the form of a solid by distilling off the solvent under heating and reduced pressure as described in Example 2

[0139] MIR-3000: Biphenyl aralkyl type maleimide resin (manufactured by Nippon Kayaku Co., Ltd.)

[0140] NC-3000-L: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)

[0141] GPH-65: Biphenyl aralkyl type phenol resin (manufactured by Nippon Kayaku Co., Ltd.)

[0142] 2E-4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Co., Ltd.)

[0143] From Table 1, it was confirmed that Example 2 had excellent dielectric properties and high heat resistance.

[0144] Industrial Applicability

[0145] The curable resin composition of the present invention is useful in applications such as insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.), laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.) or various composite materials represented by carbon fiber reinforced plastics (CFRP), coatings, etc.

Claims

1. A maleimide resin represented by the following formula (1): In formula (1), R represents a methyl group; m represents an integer of 1 to 4; n represents an average value, and 1≦n≦10.

2. The maleimide resin according to claim 1, which is represented by the following formula (3): In the formula, n represents the average value, and 1≦n≦10.

3. A curable resin composition comprising the maleimide resin according to claim 1 or 2.

4. A cured product obtained by curing the curable resin composition according to claim 3.

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