Aromatic amine resin, maleimide resin, curable resin composition and the cured product thereof

Abstract

The present invention aims to provide an aromatic amine resin having a specific structure with excellent solvent solubility. Furthermore, the invention aims to provide a curable resin composition containing a maleimide resin derived from an aromatic amine having a specific structure with excellent high heat resistance and low dielectric properties, which is preferably used in packaging of electrical and electronic components, circuit boards, carbon fiber composites, etc., and a cured product thereof. An aromatic amine resin represented by the following formula (1). (In formula (1), R1, R2, and R3 represent hydrocarbon groups having 1 to 18 carbon atoms. m represents an integer from 1 to 4, n is an average value, and 1 ≤ n ≤ 20.

Description

Technology Field

[0001] The present invention relates to aromatic amine resins and maleimide resins derived therefrom, curable resin compositions using these and cured products thereof, and is suitable for use in electrical and electronic components such as semiconductor encapsulating materials, printed circuit boards, and build-up laminates, or lightweight high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics. Background Technology

[0002] Recently, as the fields of application for laminated boards mounting electrical and electronic components expand, the required characteristics have become more extensive and sophisticated. While conventional semiconductor chips were predominantly mounted on metal lead frames, semiconductor chips with high processing power, such as central processing units (hereinafter referred to as CPUs), are increasingly being mounted on laminated boards made of polymer materials.

[0003] In particular, in semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like, thinning of the PKG substrate is required to meet the demands for miniaturization, thinning, and high density. However, as the PKG substrate becomes thinner, rigidity decreases, causing problems such as significant warping due to heating when soldering the PKG onto a main board (PCB). To reduce this, a PKG substrate material with a high Tg above the soldering temperature is required.

[0004] In addition, new high capacity and high-speed communication are expected to proceed in the fifth-generation communication system "5G," which is currently being accelerated in development. The need for low dielectric loss tangent materials is increasing, and a dielectric loss tangent of 0.005 or less at least at 1 GHz is required.

[0005] Furthermore, as electrification progresses in the automotive sector and precision electronic devices are sometimes placed near engine drive units, a higher level of heat and moisture resistance is required. SiC semiconductors are just beginning to be used in applications such as electric trains and air conditioners, and since very high heat resistance is required for semiconductor device encapsulation materials, conventional epoxy resin encapsulation materials cannot meet this requirement.

[0006] Against this backdrop, polymer materials capable of achieving both heat resistance and low dielectric loss tangent properties are being considered. For example, Patent Document 1 proposes a composition comprising a maleimide resin and a propenyl group-containing phenolic resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, the electrical properties cannot be considered sufficient. Also, Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are substituted with allyl groups. However, it is illustrated that a Claisen potential occurs at 190°C, and since phenolic hydroxyl groups that do not contribute to the curing reaction are generated at 200°C, which is the molding temperature of a general substrate, the electrical properties cannot be satisfied. Prior art literature

[0007] Patent Document 1: Japanese Patent Publication No. Hei 04-359911 Patent Document 2: International Publication No. 2016 / 002704 The problem to be solved

[0008] The present invention has been made in consideration of these circumstances and aims to provide an aromatic amine resin, a curable resin composition, and a cured product thereof that exhibit excellent heat resistance and electrical properties and good curability. means of solving the problem

[0009] As a result of diligent research to solve the above problem, the inventors discovered a novel aromatic amine resin. Furthermore, they discovered that a cured product of a curable resin composition containing a maleimide resin derived from an aromatic amine resin has excellent heat resistance and low dielectric properties, thereby completing the present invention.

[0010] That is, the present invention relates to the following [1] to [9].

[0011] [1] An aromatic amine resin represented by the following formula (1).

[0012] [Chemical Formula 1]

[0013]

[0014] (In Equation (1), R1, R2, and R3 represent hydrocarbon groups having 1 to 18 carbon atoms. m represents an integer from 1 to 4, n is the average value, and 1 ≤ n ≤ 20.)

[0015] [2] An aromatic amine resin described in the preceding claim [1], obtained by reacting an aniline-based compound substituted at the 2,6-position with an alkyl benzene formalin resin.

[0016] [3] An aromatic amine resin described in the preceding paragraph [1] or [2], represented by the following formula (2).

[0017] [Chemical Formula 2]

[0018]

[0019] (In Equation (2), n is the average value and represents 1 ≤ n ≤ 20.)

[0020] [4] An aromatic amine resin described in the preceding claim [3], obtained by reacting 2-ethyl-6-methylaniline with xylene formalin resin.

[0021] [5] An aromatic amine resin described in any one of the preceding [1] to [4] having a softening point of 80°C or lower.

[0022] [6] An aromatic amine resin described in any one of claims [1] to [5] having a weight average molecular weight of 300 to 700.

[0023] [7] Maleimide resin obtained by reacting an aromatic amine resin described in any one of the preceding [1] to [6] with maleic acid or maleic anhydride.

[0024] [8] A curable resin composition containing maleimide resin as described in the preceding paragraph [7].

[0025] [9] A cured product obtained by curing the curable resin composition described in the preceding paragraph [8]. Effects of the invention

[0026] The aromatic amine resin of the present invention has a sharp molecular weight distribution, so it has excellent solvent solubility and handling properties, and is also very useful as a raw material for maleimide resins, etc.

[0027] In addition, the cured product of the curable resin composition containing a maleimide resin derived from the aromatic amine resin of the present invention has excellent properties of high heat resistance and low dielectric strength, and is useful for packaging electrical and electronic components, circuit boards, carbon fiber composites, etc. Brief explanation of the drawing

[0028] [Fig. 1] The 1H-NMR chart of Example 1 is shown. [Fig. 2] The 1H-NMR chart of Example 2 is shown. Specific details for implementing the invention

[0029] The aromatic amine resin of the present invention is represented by the following formula (1).

[0030] [Chemical Formula 1]

[0031]

[0032] (In Equation (1), R1, R2, and R3 represent hydrocarbon groups having 1 to 18 carbon atoms. m represents an integer from 1 to 4, n is the average value, and 1 ≤ n ≤ 20.)

[0033] In the above formula (1), it is preferable that R1, R2, and R3 are hydrocarbon groups having 1 to 3 carbon atoms, and that m is 1 or 2.

[0034] The aromatic amine resin of the present invention is particularly preferred when represented by the following formula (2).

[0035] [Chemical Formula 2]

[0036]

[0037] (In Equation (2), n is the average value and represents 1 ≤ n ≤ 20.)

[0038] Also, n is preferably 1≤n≤10, and more preferably 1≤n≤5.

[0039] The aromatic amine resin of the present invention has the advantage of having a sharp molecular weight distribution without the weight-average molecular weight becoming excessively large. The aromatic amine of the present invention has a sharp molecular weight distribution by using aniline having a substituent on the 2,6-position as a raw material.

[0040] The weight average molecular weight of the aromatic amine of the present invention is preferably 300 to 700, and more preferably 400 to 600. The molecular weight distribution can be measured by GPC (gel penetration chromatography). When a maleimide resin is synthesized using an amine resin with a weight average molecular weight exceeding 700 as a raw material, purification by washing with water becomes difficult due to the large molecular weight and high polarity, making it difficult to remove impurities such as acid catalysts. If the weight average molecular weight is less than 300, there is a possibility that the solvent stability will decrease when used as a varnish.

[0041] The method for preparing the aromatic amine resin of the present invention is not particularly limited. For example, a 2,6-position substituted aniline-based compound and an alkylbenzene formalin resin may be reacted under an acid catalyst such as hydrochloric acid or activated clay, or a 2,6-position substituted aniline-based compound, formalin, and alkylbenzenes may be reacted under an acid catalyst such as hydrochloric acid or activated clay. In the case where hydrochloric acid is used as a catalyst, the desired aromatic amine resin can be obtained by neutralizing with an alkali metal such as sodium hydroxide or potassium hydroxide, extracting with an aromatic hydrocarbon solvent such as toluene or xylene, washing until the wastewater becomes neutral, and then distilling and removing the solvent using an evaporator or the like.

[0042] Examples of the above 2,6-substituted aniline compounds include 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-dipropylaniline, 2,6-diisopropylpropylaniline, 2-ethyl-6-methylaniline, 2-methyl-6-propylaniline, 2-isopropyl-6-methylaniline, 2-ethyl-6-propylaniline, 2-ethyl-6-isopropylaniline, etc., but are not limited to these. Since solvent solubility improves as the number of carbon atoms increases but heat resistance decreases, it is preferable that it be substituted with an alkyl group having 1 to 3 carbon atoms, more preferable that it be substituted with an alkyl group having 1 to 2 carbon atoms, and most preferable that it be 2-ethyl-6-methylaniline.

[0043] The above alkyl benzene formalin resins include toluene formalin resin, o-xylene formalin resin, m-xylene formalin resin, p-xylene formalin resin, 1,2,3-trimethylbenzene formalin resin, 1,2,4-trimethylbenzene formalin resin, 1,2,5-trimethylbenzene formalin resin, 1,3,5-trimethylbenzene formalin resin, 1,2,3,4-tetramethylbenzene formalin resin, 1,2,3,5-tetramethylbenzene formalin resin, 1,2,4,5-tetramethylbenzene formalin resin, 1,3,5-triethylbenzene formalin resin, 1,3,5-tripropylbenzene formalin resin, 1,3,5-triisopropylbenzene formalin resin, and 1,3,5-tributylbenzene Examples include formalin resin and 1,3,5-tri-t-butylbenzene formalin resin, but are not limited thereto. These may be used individually or in combination of two or more types. From the perspective of dielectric properties and heat resistance, it is preferable that they be substituted with hydrocarbon groups having 1 to 5 carbon atoms, more preferably with hydrocarbon groups having 1 to 3 carbon atoms, and even more preferably with methyl groups. As the number of carbon atoms in the hydrocarbon group increases, it becomes difficult to guarantee the rigidity of the molecule and the molecule becomes prone to vibration, which causes a decrease in dielectric properties or heat resistance. The amount of alkylbenzene formalin resin used is typically 0.05 to 0.8 weight% relative to 1 weight% of aniline used, and preferably 0.1 to 0.6 weight%.

[0044] When reacting 2-ethyl-6-methylaniline with xylene formalin resin, Lewis acids such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, aluminum chloride, zinc chloride, etc., solid acids such as activated clay, acidic clay, white carbon, zeolite, silica alumina, acidic ion exchange resin, etc. may be used as needed. These may be used individually or in combination of two or more types. From the perspective of ease of manufacturing process and economic feasibility, it is preferable to use reusable solid acids (solid acids such as activated clay, acidic clay, white carbon, zeolite, silica alumina, acidic ion exchange resin, etc.). The amount of catalyst used is typically 0.1 to 0.8 moles per mole of the 2,6-substituted aniline compound used, and preferably 0.2 to 0.7 moles. If too much is used, there is a risk that the viscosity of the reaction solution will become too high, making stirring difficult, and if too little is used, there is a risk that the progress of the reaction will be slowed down. (When using the above-mentioned reusable solid acid catalyst, the amount is 1 to 50 wt%, preferably 5 to 40 wt%, and more preferably 10 to 30 wt% relative to the amount of the injected 2,6-position substituted aniline compound. If the amount of solid acid used is greater than the above range, it is difficult to ensure the fluidity of the reaction solution, and if the amount of solid acid used is less than the above range, the reaction may not proceed sufficiently or the reaction time may be prolonged.) The reaction may be carried out using organic solvents such as toluene or xylene as needed, or it may be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of a 2,6-position substituted aniline compound, alkylbenzene formalin resin, and a solvent, if the catalyst contains water, the water is removed from the system by azeotropic boiling. After that, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours.Thereafter, while removing water or low molecular weight components generated in the system by azeotropic dehydration, the temperature is raised to 180–300°C, preferably 190–250°C, more preferably 200–240°C, and the reaction is carried out for 5–50 hours, preferably 5–20 hours. After the reaction is completed, the acidic catalyst is neutralized with an alkaline aqueous solution, and then a water-insoluble organic solvent is added to the oil layer to repeat washing until the wastewater becomes neutral (if the aforementioned reusable solid acid catalyst is used, the catalyst is removed by filtration).

[0045] The softening point of the aromatic amine resin of the present invention is preferably 80°C or lower, and more preferably 70°C or lower. If the softening point is higher than 80°C, the viscosity of the maleimidized resin increases, making it difficult to impregnate carbon fibers or glass fibers. If the viscosity is lowered by increasing the amount of diluent solvent, there is a possibility that the resin will not adhere sufficiently to the fibrous material during the impregnation process.

[0046] The maleimide resin of the present invention can be obtained by reacting maleic acid or maleic anhydride with the aromatic amine resin of the present invention in the presence of a solvent and a catalyst, for example, by adopting the method described in Japanese Patent Publication No. 6429862. In that case, since it is necessary to remove water generated during the reaction from the system, a water-insoluble solvent is used for the reaction. Examples include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester-based solvents such as ethyl acetate and butyl acetate, and ketone-based solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more types may be used in combination. In addition to the above water-insoluble solvent, a non-protonated polar solvent may also be used in combination. Examples include dimethylsulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc., and two or more types may be used in combination. When using a non-protonic polar solvent, it is preferable to use one with a higher boiling point than the water-insoluble solvent used in combination. The catalyst is not particularly limited, but acidic catalysts such as p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid may be used. 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 then p-toluenesulfonic acid is added and the reaction is carried out under reflux conditions while removing the water generated from the system.

[0047] The curable resin composition of the present invention may use any known material as a curable resin other than the maleimide resin of the present invention. Specifically, examples include phenolic resin, epoxy resin, amine resin, active alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, metallyl resin, active ester resin, etc. It is preferable to include epoxy resin, active alkene-containing resin, and cyanate ester resin due to the balance of heat resistance, adhesion, and dielectric properties. By including such curable resins, the softness of the cured product and adhesion to metal can be improved, thereby suppressing package cracks during reliability tests such as solder reflow or cold-heat cycles. The curable resin other than the maleimide resin of the present invention may be used as a single type or in combination of multiple types.

[0048] The amount of the above-mentioned curable resin used is typically less than 10 parts by mass, preferably less than 3 parts by mass, even more preferably less than 2 parts by mass, and particularly preferably less than 1.5 parts by mass with respect to the maleimide resin of the present invention. If the amount is 10 parts by mass or more, the concentration of the maleimide resin of the present invention may decrease, making it possible to obtain sufficient heat resistance or dielectric properties. In addition, the preferred lower limit is 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more.

[0049] 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, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, Polymers with diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenol resins obtained by polycondensation with 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.

[0050] Epoxy resin: the above-mentioned phenol resin, glycidyl ether-based epoxy resin obtained by glycidylating alcohols, etc., alicyclic epoxy resin represented by 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, etc., glycidylamine-based epoxy resin represented by tetraglycidyl diaminodiphenylmethane (TGDDM) or triglycidyl-p-aminophenol, etc., glycidyl ester-based epoxy resin.

[0051] Amine resin: diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, naphthalene diamine, aniline novolac, orthoethylaniline novolac, aniline resin obtained by reaction of aniline with xylylene chloride, amine resin obtained by reaction of aniline with substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) as described in Japanese Patent Publication No. 6429862, or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.).

[0052] Active alkene-containing resin: a polycondensate of the above phenol resin and an active alkene-containing halogen compound (chloromethylstyrene, allyl chloride, metallyl chloride, acrylic acid chloride, etc.), a polycondensate of an active alkene-containing phenol (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and a halogen compound (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanul chloride, etc.), a polycondensate of an epoxy resin or alcohol and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), a maleimide resin (4,4'-diphenylmethanebismaleimide, Polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonibsmaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene).

[0053] Isocyanate resins: aromatic diisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene 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 one or more biuret bodies of isocyanate monomers or isocyanate bodies obtained by trimerizing the above diisocyanate compounds; Polyisocyanate obtained by a urethane reaction between the above isocyanate compound and a polyol compound.

[0054] Polyamide resin: amino acids (6-aminocaproic acid, 11-aminoundecanic acid, 12-aminododecanoic acid, para-aminomethyl benzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and diamines (aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decandiamine, undecandiamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecandiamine, nonadecandiamine, eicosandiamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, etc.; cyclohexanediamine, A mixture of one or more selected from the group comprising alicyclic diamines such as bis-(4-aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylenediamine; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, souveric acid, azelaic acid, sebacic acid, undecandeiacid, dodecandeiacid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoiisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and dichlorides, as a main raw material Polymer.

[0055] Polyimide resin: the above diamine and tetracarboxylic acid dianhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid Dehydrogenates, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-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)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-Bis(3,4-Dicarboxyphenoxy)benzene dianhydride, 1,3-Bis[2-(3,4-Dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-Bis[2-(3,4-Dicarboxyphenyl)-2-propyl]benzene dianhydride, 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 acid dianhydride, 1,4,5,8-Naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-Naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-Perylenetetracarboxylic acid dianhydride, 2,3,6,7-Anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride), cyclopentane tetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic acid 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-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid)dianhydride, 2,2-propylidene-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]octo-7-en-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S, 5R, Polycondensation compounds with 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 acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl)ether, 4,4'-biphenylbis(trimellitic acid monoester anhydride), and 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride).

[0056] Cyanate ester resin: A cyanate ester compound obtained by reacting a phenol resin with a cyanide halide. Specific examples include, but are not limited to, dicyanatebenzene, tricyanatebenzene, dicyanatenaphthalene, dicyanatebiphenyl, 2,2'-bis(4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis(4-cyanatephenyl)thioether, phenol novolaxianate, and a phenol dicyclopentadiene cocondensate in which the hydroxyl group is converted to a cyanate group.

[0057] In addition, the cyanate ester compound for which the synthesis method is described in Japanese Patent Publication No. 2005-264154 is particularly desirable as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0058] The cyanate resin may, if necessary, contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, or dibutyl tin maleate to trimerize the cyanate group and form a sym-triazine ring. The catalyst is typically 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 mass of the thermosetting resin composition.

[0059] Active ester compound: As a curing agent for curable resins other than the essential components described in the present invention, such as epoxy resins, a compound having one or more active ester groups per molecule may be used as needed. As an active ester-based curing agent, compounds having two or more ester groups with high reaction activity per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred. The active ester-based curing agent is preferably obtained by a condensation reaction between at least one compound selected from carboxylic acid compounds and thiocarboxylic acid compounds and at least one compound selected from hydroxy compounds and thiol compounds. In particular, from the perspective of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from at least one compound selected from a carboxylic acid compound, a phenol compound, and a naphthol compound is preferred.

[0060] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.

[0061] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolnaphthalene, 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, fluoroglucan, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

[0062] Preferred embodiments of an active ester-based curing agent include an active ester compound comprising a dicyclopentadiene-type diphenol structure, an active ester compound comprising a naphthalene structure, an active ester compound comprising an acetylated compound of phenol novolac, and an active ester compound comprising a benzoylated compound of phenol novolac. Among these, an active ester compound comprising a naphthalene structure and an active ester compound comprising a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene, dicyclopentylene, and phenylene.

[0063] Commercially available active ester-based 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", and "EXB-8150-65T" (manufactured by DIC); active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC); active ester compounds containing an acetylated form of phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical); and active ester compounds containing a benzoylated form of phenol novolac such as "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical). Examples include "DC808" (manufactured by Mitsubishi Chemical) as an active ester-based curing agent that is an acetylated compound of phenol novolak; and "EXB-9050L-62M" (manufactured by DIC) as an active ester-based curing agent containing phosphorus.

[0064] In the curable resin composition of the present invention, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of a radically polymerizable curable resin, such as maleimide resin, or radical polymerization with other components. As usable radical polymerization initiators, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)-benzene; peroxyketals such as t-butylperoxybenzoate and 1,1-di-t-butylperoxycyclohexane; α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyfivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5, Known compounds such as alkyl peresters including 5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate; peroxycarbonates including di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropylcarbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane; organic peroxides including t-butylhydroperoxide, cumenehydroperoxide, t-butylperoxyoctoate, and lauroyl peroxide; or azo compounds including azobis(isobutyronitrile), 4,4'-azobis(4-cyanogylacetic acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). Radical polymerization initiators may be used, but are not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, and dialkyl peroxides are more preferred. As for the amount of radical polymerization initiator added, 0.01 to 5 parts by mass per 100 parts by mass of the curable resin composition is preferred, and 0.01 to 3 parts by mass is particularly preferred.If a large amount of radical polymerization initiator is used, the molecular weight is not sufficiently elongated during the polymerization reaction.

[0065] In the curable resin composition of the present invention, a curing accelerator (curing catalyst) may be used in combination as needed. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol or 1,8-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium 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 not specifically designated as a halogen, organic acid ion, hydroxide ion, etc., but organic acid ions and hydroxide ions are particularly preferred), and tin octylate. Examples include transition metal compounds (transition metal salts), such as zinc compounds like zinc carboxylates (zinc 2-ethylhexanate, zinc stearate, zinc behenate, zinc myristate) or zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate, etc.). The amount of curing accelerator used is 0.01 to 5.0 parts by weight per 100 parts by weight of epoxy resin, depending on the need.

[0066] The curable resin composition of the present invention may include a phosphorus-containing compound as a flame-retardant imparting component. The phosphorus-containing compound may be of a reactive type or an additive type. Specific examples of phosphorus-containing compounds include phosphate esters such as trimethylphosphate, triethylphosphate, tricresylphosphate, trixyllenylphosphate, cresyl diphenylphosphate, cresyl-2,6-dicylenylphosphate, 1,3-phenylenebis(dicylenylphosphate), 1,4-phenylenebis(dicylenylphosphate), and 4,4'-biphenyl(dicylenylphosphate); and phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Examples include phosphorus-containing epoxy compounds obtained by reacting the epoxy resin with the active hydrogen of the phosphanes, red phosphorus, etc., but phosphate esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dicyllenyl phosphate), 1,4-phenylenebis(dicyllenyl phosphate), 4,4'-biphenyl(dicyllenyl 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) / (pre-epoxy resin) of 0.1 to 0.6 (weight ratio). At 0.1 or less, flame retardancy is insufficient, and at 0.6 or more, there is a risk of adverse effects on the hygroscopicity and dielectric properties of the cured product.

[0067] In addition, an antioxidant may be added to the curable resin composition of the present invention as needed. Suitable antioxidants include phenolic, sulfur-based, and phosphorus-based antioxidants. The antioxidant may be used alone or in combination of two or more types. The amount of antioxidant used is typically 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the resin component in the curable resin composition of the present invention. While each of these antioxidants may be used individually, it is acceptable to use two or more types in combination. In particular, phosphorus-based antioxidants are preferred in the present invention.

[0068] Specific examples of phenolic antioxidants include monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol, etc.; 2,2'-Methylenebis(4-methyl-6-t-butylphenol), 2,2'-Methylenebis(4-ethyl-6-t-butylphenol), 4,4'-Thiobis(3-methyl-6-t-butylphenol), 4,4'-Butylidenebis(3-methyl-6-t-butylphenol), Triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-Hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2-Thio-Diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Bisphenols such as 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl)calcium; 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, High molecular weight phenols such as tocopherol are examples.

[0069] Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc.

[0070] Specific examples of phosphorus-based antioxidants include phosphites such as triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl)phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbi(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbi(2,4-di-t-butyl-4-methylphenyl)phosphite, and bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogenphosphite; Examples of oxaphosphaphenanthren oxides include 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide.

[0071] In addition, a light stabilizer may be added to the curable resin composition of the present invention as needed. Hindered amine-based light stabilizers, particularly HALS, are suitable as light stabilizers. HALS are not particularly limited, but representative examples include the 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, the polycondensate of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine 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{(2,2,6, Examples include 6-tetramethyl-4-piperidyl)imino], bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), etc. There is. Only one type of HALS may be used, or two or more types may be used in combination.

[0072] In addition, a binder resin may be incorporated into the curable resin composition of the present invention as needed. Examples of binder resins include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin, etc., but are not limited to these. The amount of binder resin incorporated is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is typically used in an amount of 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass, per 100 parts by mass of the resin component as needed.

[0073] In addition, the curable resin composition of the present invention may, as needed, add powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide, asbestos, glass powder, or inorganic fillers formed into spherical or crushed forms. Furthermore, particularly when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is typically in the range of 80 to 92 mass%, preferably 83 to 90 mass%, of the curable resin composition.

[0074] Known additives may be incorporated into the curable resin composition of the present invention as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluoropolymer, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, release agents, and coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives incorporated is preferably in the range of 1,000 parts by weight or less, more preferably 700 parts by weight or less, per 100 parts by weight of the curable resin composition.

[0075] The curable resin composition of the present invention can be obtained by uniformly mixing each of the above components in a predetermined ratio, and typically pre-cured at 130 to 180°C for 30 to 500 seconds, and further post-cured at 150 to 200°C for 2 to 15 hours, thereby allowing a sufficient curing reaction to proceed and obtaining the cured product of the present invention. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent, etc., and then cured after removing the solvent.

[0076] The curable resin composition of the present invention obtained in this manner possesses moisture resistance, heat resistance, and high adhesion. Therefore, the curable resin composition of the present invention can be utilized in a wide range of fields requiring moisture resistance, heat resistance, and high adhesion. Specifically, it is useful as a material for electrical and electronic components, such as insulating materials, laminates (printed circuit boards, BGA substrates, build-up substrates, etc.), encapsulation materials, and resists. In addition to molding materials and composite materials, it can also be used in fields such as paint materials and adhesives. In particular, for semiconductor encapsulation, resistance to solder reflow is beneficial.

[0077] The semiconductor device has a curable resin composition of the present invention. Examples of 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), TQFP (Thin Quad Flat Package), etc.

[0078] The method for preparing the curable resin composition of the present invention is not particularly limited, but may be performed simply by uniformly mixing each component or by prepolymerizing. For example, the curable resin of the present invention may be prepolymerized by heating in the presence or absence of a catalyst, or in the presence or absence of a solvent. Similarly, in addition to the curable resin of the present invention, it may be prepolymerized by adding a curing agent such as an epoxy resin, amine compound, maleimide-based compound, cyanate ester compound, phenol resin, acid anhydride compound, and other additives. For mixing each component or prepolymerizing, an extruder, kneader, roller, etc., may be used in the absence of a solvent, and a reaction kettle equipped with a stirring device may be used in the presence of a solvent.

[0079] As a method for uniform mixing, the resin composition is mixed to form a uniform resin composition by using a device such as a kneader, roller, or planetary mixer at a temperature within the range of 50 to 100°C. The obtained resin composition may be ground and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or into a granular powder or powder-shaped molded body, or the composition may be melted on a surface support and molded into a sheet shape with a thickness of 0.05 mm to 10 mm to form a curable resin composition molded body. The obtained molded body is a non-sticky molded body at 0 to 20°C and does not significantly reduce fluidity or curability even when stored at 25 to 0°C for more than one week.

[0080] The obtained molded body can be formed into a cured product using a transfer molding machine or a compression molding machine.

[0081] An organic solvent may be added to the curable resin composition of the present invention to form a varnish-type composition (hereinafter simply 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, or N-methylpyrrolidone as needed to form a varnish, and impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and then heat-dried to obtain a prepreg, which may be then heat-press molded to obtain a cured product of the curable resin composition of the present invention. At this time, the solvent is used in an amount that typically accounts for 10 to 70 weight percent, preferably 15 to 70 weight percent, of the mixture of the curable resin composition of the present invention and the corresponding solvent. In addition, if the composition is in a liquid state, a curable resin product containing carbon fiber may be obtained as is, for example, by the RTM method.

[0082] Furthermore, 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 in the B-stage. Such a film-type resin composition can be obtained as a sheet-type adhesive by applying the curable resin composition of the present invention as a curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-type adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

[0083] The curable resin composition of the present invention can be heated, melted, and reduced in viscosity to obtain prepregs by impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Specific examples include, for instance, 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; furthermore, inorganic fibers other than glass, polyparaphenyleneterephthalamide (Kevlar (registered trademark), manufactured by DuPont Corp.), fully aromatic polyamides, polyesters; and organic fibers such as polyparaphenylenebenzoxazole, polyimide, and carbon fibers, but are not particularly limited thereto. The shape of the substrate is not particularly limited, but examples include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, etc. In addition, plain weave, basket weave, twill weave, etc., are known methods for weaving fabrics, and these known methods can be appropriately selected and used according to the intended use or performance. Furthermore, glass woven fabrics that have been treated with an opening process or surface-treated with a silane coupling agent are preferably used. The thickness of the substrate is not particularly limited, but is preferably about 0.01 to 0.4 mm. In addition, prepreg can be obtained by impregnating reinforcing fibers with the above varnish and heating and drying them.

[0084] The laminate of the present embodiment comprises one or more of the prepregs. As long as the laminate comprises one or more prepregs, it is not particularly limited and may have any other layers. As for the method of manufacturing the laminate, generally known methods can be appropriately applied and are not particularly limited. For example, when forming a metal foil laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., may be used, and the laminate can be obtained by laminating the prepregs together and heat-pressuring them. At this time, the heating temperature is not particularly limited, but 65 to 300°C is preferred, and 120 to 270°C is more preferred. In addition, the pressure applied is not particularly limited, but if the pressure is excessively high, it is difficult to control the solid content of the resin in the laminate, resulting in unstable quality, and if the pressure is excessively low, bubbles or poor adhesion between layers occur; therefore, 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of the present embodiment can be preferably used as a metal foil laminate described later by having a layer made of metal foil.

[0085] The above prepreg can be cut into a desired shape and laminated with copper foil, etc., as needed, and then a curable resin composition is heat-cured while applying pressure to the laminate using a press molding method, an autoclave molding method, or a sheet winding molding method to obtain an electrical and electronic laminate (printed circuit board) or a carbon fiber reinforcement.

[0086] 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 described in the present invention exhibits excellent heat resistance and dielectric properties, it is preferably used in electrical and electronic components such as encapsulating materials for semiconductor devices, encapsulating materials for liquid crystal display devices, encapsulating materials for organic EL devices, printed circuit boards, and build-up laminates, or in composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

[0087] Examples

[0088] Next, the present invention will be explained in more detail by way of examples. Unless otherwise specifically stated, parts are by weight. Furthermore, the present invention is not limited to these examples.

[0089] The various analysis methods used in the examples are described below.

[0090] <Amine Equivalent>

[0091] The value obtained in accordance with Annex A of JIS K-7236 (Correction method for glycidylamine) was taken as the amine equivalent.

[0092] <Yeonhwajeom>

[0093] Measured in accordance with JIS K-7234.

[0094] <ICI Viscosity (150℃)>

[0095] Measured in accordance with JIS K-7117-2.

[0096] <Weight Average Molecular Weight (Mw)>

[0097] It was calculated by polystyrene conversion using a polystyrene standard solution.

[0098] GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

[0099] Columns: Shodex KF-603, KF-602x2, KF-601x2)

[0100] Linking eluent: Tetrahydrofuran

[0101] Flow rate: 0.5 ml / min.

[0102] Column temperature: 40℃

[0103] Detection: RI (Refraction detector)

[0104] [Example 1]

[0105] 198 parts of xylene formalin resin (manufactured by Nikanol G Hood Co., Ltd.), 622 parts of 2-ethyl-6-methylaniline (manufactured by Tokyo Kasei Co., Ltd.), 300 parts of toluene, and 82 parts of activated clay (manufactured by Japan Activated Clay Co., Ltd.) were added to a flask equipped with a thermometer, a condenser, a Dean Stark azeotropic distillation trap, and a stirrer. After reacting at 120°C for 1 hour, the effluent was withdrawn, and the temperature was raised to 150°C and maintained for 4 hours. Subsequently, the temperature was raised to 200°C and the reaction was carried out at 200°C for 10 hours. After cooling, the activated clay was removed by filtration after diluting with 300 parts of toluene, and the solvent and excess 2-ethyl-6-methylaniline were removed by distillation under reduced pressure to obtain 315 parts of aromatic amine resin (A1) (softening point: 65°C, melt viscosity: 0.13 Pa·s, amine equivalent: 199 g / eq, Mw: 581). The 1H-NMR chart of the obtained amine resin is shown in FIG. 1.

[0106] 1H-NMR (400 MHz, DMSO-d6); δ(ppm) 0.92-1.18(m, 221H), 1.88-2.46(m, 611H), 3.48-3.98(m, 124H), 4.21-4.38(m, 127H), 5.33(s, 4H), 6.30-6.70(m, 156H), 6.82-7.02(m, 35H), 7.23(s, 4H)

[0107] [Example 2]

[0108] 221 parts of maleic anhydride (manufactured by Tokyo Kasei Co., Ltd.) and 100 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer, and heated. After cooling and separating the water and toluene that formed an azeotrope, only the organic layer, toluene, was returned to the system for dehydration. Next, 300 parts of the aromatic amine resin (A1) obtained in Example 1 were dissolved in a mixed solvent of 50 parts of N-methyl-2-pyrrolidone and 150 parts of toluene, and a resin solution was added dropwise over 1 hour while maintaining the system at 80–85°C. After the dropwise addition was finished, the reaction was carried out for 2 hours at the same temperature, and 6 parts of p-toluenesulfonic acid were added. After cooling and separating the condensed water and toluene that formed an azeotrope under reflux conditions, only the organic layer, toluene, was returned to the system for dehydration while the reaction was carried out for 20 hours. After the reaction was finished, 600 parts of toluene were added and repeated washing with water was performed to remove p-toluenesulfonic acid and excess maleic anhydride, and the water was removed from the system by heating through azeotropy. Next, 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 the maleimide resin (M1) was 827. The 1H-NMR chart of the solid extract (M1') of the maleimide resin (M1) by reduced pressure concentration is shown in FIG. 2.

[0109] 1H-NMR (400 MHz, DMSO-d6); δ (ppm) 0.80-1.10 (m, 7H), 1.75-2.40 (m, 20H), 3.61-4.28 (m, 4H), 6.59-7.18 (m, 6H), 7.25 (d, 4H)

[0110] [Comparative Example 1]

[0111] 210 parts of xylene formalin resin (manufactured by Nikanol G Hood Co., Ltd.), 738 parts of aniline (manufactured by Tokyo Kasei Co., Ltd.), 100 parts of toluene, and 95 parts of activated clay were placed in a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer. After reacting at 120°C for 1 hour, the effluent was removed, and the temperature was raised to 150°C and maintained for 4 hours. Afterward, the temperature was raised to 200°C and reacted at 200°C for 10 hours. After cooling, the mixture was diluted with 300 parts of toluene, and the activated clay (manufactured by Japan Activated Clay Co., Ltd.) was removed by filtration. Then, the solvent and excess aniline were removed by distillation under reduced pressure, thereby obtaining 314 parts of aromatic amine resin (A2) (softening point: 66.6°C, melt viscosity: 0.23 Pa·s, amine equivalent: 198 g / eq, Mw: 734).

[0112] [Comparative Example 2]

[0113] 186 parts of maleic anhydride (manufactured by Tokyo Kasei Co., Ltd.) and 250 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer, and heated to cool and separate the azeotropic water and toluene, after which only the organic layer, toluene, was returned to the system to perform dehydration. Next, a resin solution obtained by dissolving 250 parts of the aromatic amine resin (A2) obtained in Comparative Example 1 in a mixed solvent of 250 parts of N-methyl-2-pyrrolidone and 250 parts of toluene was added dropwise over 1 hour while maintaining the system at 80–85°C. After the dropwise addition was finished, the reaction was carried out for 2 hours at the same temperature, and 5 parts of p-toluenesulfonic acid (manufactured by Tokyo Kasei Co., Ltd.) were added. Under reflux conditions, the azeotropic condensed water and toluene were cooled and separated, and only the organic layer, toluene, was returned to the system to perform dehydration while the reaction was carried out for 20 hours. After the reaction was finished, 500 parts of toluene were added and washing was performed, but the liquid separated into three layers and could not be extracted.

[0114] [Comparative Example 3]

[0115] The same reaction as in Comparative Example 2 was carried out, and after the reaction was finished, 3,000 parts of toluene and 300 parts of N-methyl-2-pyrrolidone were added and water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and water was removed from the system by heating by azeotropy. Next, the reaction solution was concentrated to obtain a resin solution containing 70% by weight of maleimide resin (M2). The weight-average molecular weight (Mw) of the maleimide resin (M2) was 1204.

[0116] It was confirmed that the aromatic amine resin (A1) obtained in Example 1 has a smaller weight-average molecular weight and a sharper molecular weight distribution compared to the aromatic amine resin (A2) obtained in Comparative Example 2. Since the aromatic amine resin (A2) has a weight-average molecular weight exceeding 700, the maleimide resin (M2) obtained from the aromatic amine resin (A2) is difficult to purify with the conventional washing method shown in Comparative Example 2 due to the size of its molecular weight and high polarity, and impurities such as acid catalysts cannot be removed. As shown in Comparative Example 3, the maleimide resin (M2) cannot be cleaned without using a large amount of organic solvent and, furthermore, using a high-polarity, high-boiling point solvent in combination. Therefore, there is a problem with high-boiling point solvents remaining in the maleimide resin, and the aromatic amine resin (A1) can be considered superior in terms of reducing industrial waste, improving yield from the same equipment, and simplifying the production process.

[0117] [Examples 3, Comparative Examples 4, 5]

[0118] The maleimide compound (M1) obtained in Example 2 was solidified by reduced pressure concentration (M1'), BMI-2300: aniline novolak type maleimide compound (manufactured by Daiwa Chemical Industry Co., Ltd.), biphenyl-aralkyl type epoxy resin (NC-3000-L manufactured by Nippon Explosives Co., Ltd.), biphenyl-aralkyl type phenol resin (KAYAHARD GPH-65 manufactured by Nippon Explosives Co., Ltd.), and 2E-4MZ (2-ethyl-4-methylimidazole manufactured by Shikoku Chemical Co., Ltd.) as a curing accelerator were mixed in the ratio (parts by mass) of Table 1, heated and melted in a metal container, poured directly into a mold, and cured at 220°C for 2 hours.

[0119] [Example 4]

[0120] The maleimide compound (M1) obtained in Example 2, solidified by vacuum concentration (M1'), and dicumyl peroxide (gunpowder axoside) were mixed in the ratio (parts by mass) of Table 1, heated and melted in a metal container, poured directly into a mold, and cured at 220°C for 2 hours.

[0121] The results of measuring the physical properties of the cured product obtained in this way for the following items are shown in Table 1.

[0122] <Heat Resistance Test>

[0123] · Glass transition temperature: The temperature at which tanδ reaches its maximum value, measured by a dynamic viscoelasticity tester.

[0124] Dynamic Viscoelasticity Tester: TA-instruments DMA-2980

[0125] Heating rate: 2℃ / min

[0126] <Permittivity Test · Dielectric Loss Tangent Test>

[0127] · Tests were performed using the cavity resonator perturbation method with a 1 GHz cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd. However, the test was conducted with a sample size of 1.7 mm in width × 100 mm in length and a thickness of 1.7 mm.

[0128] Mixing amount Example 3 Example 4 Comparative Example 4 Comparative Example 5 Maleimide compound M1' 100 100 BMI-2300 100 radical polymerization initiator DCP 0.5 0.5 Epoxy resin NC-3000-L 44 48 Phenol hardener GPH-65 32 35 Imidazole 2E-4MZ 2 1.2 Evaluation test results glass transition temperature ℃ 248 350 or more 141 350 or more permittivity % 2.8 2.6 3.1 3.0 hereditary jeopardy 0.007 0.003 0.018 0.005

[0129] M1': A solid obtained by removing the maleimide resin described in Example 2 through solvent distillation under heated reduced pressure.

[0130] BMI-2300: Aniline novolak-type maleimide compound (manufactured by Daiwa Chemical Industry Co., Ltd.)

[0131] DCP: Dicumyl peroxide (gunpowder aqueous agent)

[0132] NC-3000-L: Biphenyl-aralkyl type epoxy resin (manufactured by Japan Explosives Co., Ltd.)

[0133] GPH-65: Biphenyl-aralkyl type phenol resin (manufactured by Japan Explosives Co., Ltd.)

[0134] 2E-4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co.)

[0135] In Table 1, it was confirmed that Examples 3 and 4 have high heat resistance and also excellent dielectric properties. Industrial applicability

[0136] The curable resin composition of the present invention is useful for insulating materials for electrical and electronic components (high-reliability semiconductor encapsulation materials, etc.), laminates (printed circuit boards, substrates for BGA, build-up substrates, etc.), adhesives (conductive adhesives, etc.), various composite materials including CFRP, paints, etc.

Claims

Claim 1 Maleimide resin obtained by reacting an aromatic amine resin represented by the following formula (1) with maleic acid or maleic anhydride. In Equation (1), R1 represents an ethyl group, R2 represents a methyl group, and R3 represents a methyl group. m represents an integer from 1 to 4, n is the average value, and 1 ≤ n ≤ 20. Claim 2 A maleimide resin, which is an aromatic amine resin obtained by reacting an aniline-based compound substituted at the 2,6-position with an alkylbenzene formalin resin, wherein the aromatic amine resin represented by formula (1) is a maleimide resin. Claim 3 Maleimide resin obtained by reacting an aromatic amine resin represented by the following formula (2) with maleic acid or maleic anhydride. In equation (2), n is the average value and represents 1 ≤ n ≤ 20. Claim 4 In claim 3, the maleimide resin is an aromatic amine resin represented by formula (2) obtained by reacting 2-ethyl-6-methylaniline with xylene formalin resin. Claim 5 A maleimide resin according to claim 1 or claim 3, wherein the softening point of the aromatic amine resin represented by formula (1) or the aromatic amine resin represented by formula (2) is 80°C or lower. Claim 6 A maleimide resin according to claim 1 or claim 3, wherein the weight average molecular weight of the aromatic amine resin represented by formula (1) or the aromatic amine resin represented by formula (2) is 300 to 700. Claim 7 A curable resin composition containing maleimide resin as described in claim 1 or claim 3. Claim 8 A cured product obtained by curing the curable resin composition described in claim 7. Claim 9 delete

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