TW202237572A - Epoxy resin and production method therefor, curable resin composition, and cured product thereof - Google Patents

Abstract

The present invention provides an epoxy resin and an epoxy resin composition, cured products of which have excellent low water absorption and high elasticity. This epoxy resin is represented by formula (1). (In formula (1), n is the number of repetitions and the average thereof is 1 < n < 20. R represents a substituent represented by formula (2). Each p represents a real number of 0 to 4, and the average value of p is 0.5 to 1.5.) (In formula (2), * represents the portion bonded to an aromatic ring in formula (1). X represents a hydrogen atom or a hydrocarbon group having 1-6 carbon atoms. q represents a real number of 0 to 5.).

Description

Epoxy resin, method for producing same, curable resin composition, and cured product thereof

The present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product of the curable resin composition.

Epoxy resins are widely used in casting moldings, laminates, and integrated circuits due to their excellent electrical properties (dielectric constant/dielectric loss tangent, insulation), mechanical properties, adhesiveness, and thermal properties (heat resistance, etc.) Electrical/electronic fields such as integrated circuit (IC) sealing materials, structural materials, adhesives, coatings, etc.

In recent years, in the field of electrical/electronics, it is required to improve the flame retardancy, moisture resistance, adhesiveness, dielectric properties, etc. of the resin composition, to increase its purity, and to use it as a filler (inorganic filler or organic filler) Further improvement of various characteristics such as low viscosity for high filling and improved reactivity for shortening molding cycle (Patent Document 1). In addition, as structural materials, materials that are lightweight and have excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. Especially in the field of semiconductor sealing and substrate (substrate itself or its surrounding materials), as the semiconductor changes, it becomes complicated due to thinning, stacking, systemization, and three-dimensionalization, and a very high level of heat resistance is required. Requirements such as stability or high fluidity.

As an application example of epoxy resin in structural materials, carbon fiber reinforced plastic (carbon fiber reinforced plastic, CFRP) can be cited. CFRP is used in matrix resins for aircrafts by making use of the characteristics of lightweight and high-strength moldings. Generally, materials such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetraglycidyldiaminodiphenylmethane, etc. are used as resins used for matrix resins such as CFRP. In addition, for aircraft applications, glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane are used.

In recent years, the properties required for CFRP have become stricter, and high heat resistance is required when applied to structural materials such as aerospace applications and vehicles (Patent Document 2). Glycidylamine-based materials have high heat resistance, but have a high water absorption rate, and there is a problem of deterioration of properties after water absorption. On the other hand, general glycidyl ether-type epoxy resins have relatively low water absorption, but have a problem of low modulus of elasticity. Therefore, a material with high heat resistance and high modulus of elasticity and low water absorption is required. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-147854 [Patent Document 2] International Publication No. 2010/204173

[Problem to be Solved by the Invention]

In view of the above problems, the present invention aims to provide an epoxy resin and an epoxy resin composition whose cured product is excellent in low water absorption and high elasticity. [Means to solve the problem]

The inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to the following [1] to [7]. In addition, in this application, "(numerical value 1) - (numerical value 2)" means that an upper limit and a lower limit are included. [1] An epoxy resin represented by the following formula (1).

[chemical 1]

(In the formula (1), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (2). p represents a real number of 0 to 4, and the average value of p is 0.5～1.5.)

[Chem 2]

(In formula (2), * represents a bonding portion with the aromatic ring of formula (1). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)

[2] An epoxy resin represented by the following formula (3).

[Chem 3]

(In formula (3), n is the number of repetitions, and its average value is 1<n<20.)

[3] The epoxy resin as described in item [1] or [2] above, wherein the weight average molecular weight obtained by gel permeation chromatography (GPC) is 400-3000. [4] A curable resin composition containing the epoxy resin according to any one of [1] to [3]. [5] The curable resin composition as described in [4] above further contains an amine-based curing agent. [6] A hardened product obtained by hardening the curable resin composition described in [4] or [5] above. [7] A kind of manufacture method of epoxy resin, is the manufacture method of epoxy resin as described in any one in preceding item [1] to [3], comprises: make the polycondensate of dicyclopentadiene compound and phenolic compound and a step of reacting an indene derivative to obtain a phenol resin; and a step of epoxidizing the phenol resin. [Effect of the invention]

The present invention relates to an epoxy resin having a specific structure, a curable resin composition and a cured product of the curable resin composition, and the cured product has low water absorption and high elasticity. Therefore, the present invention can be effectively used for insulating materials for electric and electronic parts (high-reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), or various composite materials represented by CFRP, adhesives, and paints. waiting.

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention is represented by the following formula (1).

[chemical 4]

(In the formula (1), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (2). p represents a real number of 0 to 4, and the average value of p is 0.5～1.5.)

[chemical 5]

(In formula (2), * represents a bonding portion with the aromatic ring of formula (1). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)

In the formula (1), the average value of n can be obtained from the number average molecular weight obtained by measuring the gel permeation chromatography (GPC, detector: RI (refractive index)), or the isolated The average value of n is further preferably 1<n<10, particularly preferably 1<n<5.

The substituent R of the epoxy resin represented by the above formula (1) is represented by the above formula (2), and X is more preferably a hydrogen atom.

In the formula (1), p represents a real number of 0 to 4, respectively, and the average value of p is preferably 0.5 to 2.0, more preferably 0.5 to 1.5, particularly preferably 0.8 to 1.2. When the average value of p is 0.5 or more, it is easy to show a high modulus of elasticity and low water absorption, and when the average value of p is 2.0 or less, a significant increase in viscosity and a significant decrease in heat resistance can be suppressed.

An example of a preferable structure of the epoxy resin represented by the above formula (1) includes an epoxy resin represented by the following formula (3).

[chemical 6]

(In formula (3), n is the number of repetitions, and its average value is 1<n<20.)

The preferred range of n in the formula (3) is the same as that of the formula (1).

The production method of the epoxy resin of the present invention is not particularly limited, for example, it can be obtained by adding or ring-closing a phenol resin represented by the following formula (4) and an epihalohydrin in the presence of a solvent or a catalyst. .

[chemical 7]

(In formula (4), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (5). p represents a real number of 0 to 4, and the average value of p is 0.5～1.5.)

[chemical 8]

(In formula (5), * represents a bonding part with the aromatic ring of formula (4). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)

The preferred ranges of n, p, q, R, and X in the formula (4) and formula (5) are the same as those in the formula (1) and formula (2).

Here, the method for producing the phenol resin represented by the formula (4) will be described. The method for producing the phenol resin represented by the formula (4) is not particularly limited. For example, by reacting a benzylation agent such as indene or indenol with a dicyclopentadiene type phenol resin (a polycondensation product of a dicyclopentadiene compound and a phenolic compound) in the presence of an acid catalyst, the target compound can be obtained. Phenolic resin. Compared with benzylation agents such as benzyl alcohol, modification by indene derivatives such as indene or indenol increases the rigidity of the molecule, so it is possible to exhibit a high modulus of elasticity, Low water absorption.

The acidic catalyst used when synthesizing the phenol resin represented by the above formula (4) includes hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, Activated clay, ion exchange resin, etc. These may be used alone or in combination of two or more. The amount of the catalyst used is 0.1% to 50% by weight, preferably 1% to 30% by weight, with respect to the phenolic hydroxyl group used. If it is too much, waste will increase, and if it is too small, the reaction will slow down. .

If necessary, organic solvents such as toluene and xylene may be used for the reaction, or the reaction may be performed without a solvent. For example, after adding an acidic catalyst to a mixed solution of a phenol resin obtained from a polycondensate of a dicyclopentadiene compound and a phenolic compound and a benzylation agent, if the catalyst contains water, it is preferable to use Water was removed from the system by azeotropy. Then, the temperature is raised while removing the solvent from the system, and the reaction is carried out at 100° C. to 220° C., preferably 120° C. to 180° C., for 1 hour to 50 hours, preferably 2 hours to 20 hours. When an alcohol-based benzylation agent is used, water is by-produced, so water and the solvent are azeotropically removed from the system when the temperature is raised. After the reaction is over, neutralize the acidic catalyst with an aqueous alkali solution, etc., then add a non-water-soluble organic solvent to the oil layer, wash with water repeatedly until the waste water becomes neutral, and then dissolve the solvent and excess benzylation agent under heating and reduced pressure. remove. In the case of using activated clay or ion exchange resin, the reaction liquid is filtered after the reaction to remove the catalyst.

Next, the production method of the epoxy resin of this invention is demonstrated. As mentioned above, the preparation method of the epoxy resin of the present invention is not particularly limited, for example, by adding the phenol resin represented by the formula (4) and the epihalohydrin in the presence of a solvent or a catalyst, or obtained by a ring-closing reaction. The amount of epihalohydrin used is usually 1.0 to 20.0 moles, preferably 1.5 to 10.0 moles per 1 mole of the phenolic hydroxyl group of the phenol resin.

Sodium hydroxide, potassium hydroxide, etc. are mentioned as an alkali metal hydroxide which can be used for an epoxidation reaction. The alkali metal hydroxide may be a solid substance, and its aqueous solution may also be used. In the case of using an aqueous solution, the following method can be used: the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and then separated. Liquid to remove water, so that the epihalohydrin is continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.9 to 2.5 moles, preferably 0.95 to 1.5 moles per 1 mole of the phenolic hydroxyl group of the phenol resin. When the usage-amount of alkali metal hydroxide is small, reaction will not fully progress. On the other hand, excessive use of the alkali metal hydroxide exceeding 2.5 mol with respect to 1 mol of the phenolic hydroxyl group of the phenolic resin leads to unnecessary waste by-product.

In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzyl ammonium chloride may be added as a catalyst. The usage-amount of a quaternary ammonium salt is 0.1 g-15 g normally with respect to 1 mole of phenolic hydroxyl groups of a phenol resin, Preferably it is 0.2 g-10 g. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained. If the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin will increase, which may also cause deterioration of electrical reliability.

In the epoxidation reaction, it is preferable to add alcohols such as methanol, ethanol, and isopropanol, and aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran, and dioxane in terms of reaction progress. Wait for the reaction. When alcohols are used, the amount used is usually 2% by weight to 50% by weight, preferably 4% by weight to 20% by weight, based on the amount of epihalohydrin used. Moreover, when using an aprotic polar solvent, the usage-amount with respect to an epihalohydrin is normally 5 weight% - 100 weight%, Preferably it is 10 weight% - 80 weight%. The reaction temperature is usually 30°C to 90°C, preferably 35°C to 80°C. The reaction time is usually 0.5 hour to 100 hours, preferably 1 hour to 30 hours. After completion of the reaction, the reactant is washed with water or without washing with water, and the epihalohydrin, the solvent, and the like are removed under heating and reduced pressure. In addition, in order to make an epoxy resin with less hydrolyzable halogens, the recovered epoxy resin can also be dissolved in solvents such as toluene and methyl isobutyl ketone, and alkali metal hydrogen such as sodium hydroxide and potassium hydroxide can be added. Aqueous solutions of the oxides react to allow reliable ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the phenolic hydroxyl group of the phenolic resin used for glycidation. . The reaction temperature is usually 50°C to 120°C, and the reaction time is usually 0.5 hour to 24 hours. After the reaction, the generated salt is removed by filtration, washing with water, etc., and the solvent is distilled off under reduced pressure under heating, thereby obtaining the epoxy resin of the present invention.

The epoxy resin of the present invention is usually a semi-solid to solid resin at normal temperature, and its softening point is preferably below 100°C, more preferably below 80°C. When the softening point is higher than 100°C, the viscosity is high, and the impregnation of fibers decreases when making a prepreg. In addition, the epoxy equivalent is preferably from 200 g/eq to 1000 g/eq, more preferably from 300 g/eq to 800 g/eq, particularly preferably from 300 g/eq to 700 g/eq, most preferably from 330 g/eq g/eq～600 g/eq.

Hereinafter, the epoxy resin composition of this invention is demonstrated. In the epoxy resin composition of the present invention, the epoxy resin represented by formula (1) may be used alone or in combination with other epoxy resins. In the case of combined use, the proportion of the epoxy resin represented by formula (1) in all epoxy resins is preferably 10% by weight to 98% by weight, more preferably 20% by weight to 95% by weight, and more preferably Preferably, it is 30% by weight to 95% by weight. By making the addition amount 10 weight% or more, the improvement of an elastic modulus and low water absorption can be expressed.

Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include: bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl substituted phenol, aromatic substituted phenol, 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, etc.); said phenols with various diene compounds (dicyclopentadiene olefins, terpenes, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isopropene Pentadiene, etc.); polycondensates of said phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); said phenols Condensation products with aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.); said phenols and aromatic dichloromethyls (α,α'-dichloroxylene, dichloromethylbiphenyl etc.); polycondensation of said phenols with aromatic bis-alkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) products; polycondensates of the bisphenols and various aldehydes or glycidyl ether epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, glycidol The ester-based epoxy resin and the like are not limited to these as long as they are commonly used epoxy resins. These may be used alone, or two or more kinds may be used.

Examples of the curing agent that can be used in the epoxy resin composition of the present invention include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents. Specific examples of hardeners that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylene, 3,4'-diaminodiphenyl Phenylphenylene, 3,3'-diaminodiphenylene, 2,2'-diaminodiphenylene, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenyl Phenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4, 4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyl diphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3',5,5 '-Tetraisopropyldiphenylmethane, 4,4'-methylenebis(N-methylaniline), bis(aminophenyl)fluorene, 3,4'-diaminodiphenylether, 4,4'-Diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)benzene base] benzene, 1,3'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene Oxy)biphenyl, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, Aromatic amine compounds such as naphthalene diamine, benzidine, dimethylbenzidine, aromatic amine compounds described in Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2017/170551; 1,3-bis(aminomethyl ) cyclohexane, isophorone diamine, 4,4'-methylene bis (cyclohexylamine), norbornane diamine, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene Aliphatic amines such as methyldiamine, hexamethylenediamine, dimerdiamine, triethylenetetramine, etc. are not limited thereto, and can be used appropriately according to the properties to be imparted to the composition. In order to secure a pot life, it is preferable to use an aromatic amine, and it is preferable to use an aliphatic amine when immediate hardening property is to be imparted. By using an amine compound containing a difunctional component as a main component as a curing agent, a highly linear network can be constructed during the curing reaction, thereby exhibiting particularly excellent toughness. In addition, amide-based compounds such as dicyandiamine, polyamide resin synthesized from linolenic acid dimer and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. , maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other acid anhydride compounds ; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, Dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or said phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornadiene, norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or said phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) polycondensate, or the polycondensate of the phenols and aromatic dichloromethyls (α, α'-dichloroxylene, dichloromethylbiphenyl, etc.), or the polycondensates of the phenols and aromatic bis-alkoxy Polycondensates of methyl groups (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or polycondensates of said bisphenols and various aldehydes, and Phenolic compounds such as modified substances of these; imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc., but are not limited to these.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of epoxy groups in the epoxy resin. Favorable cured physical properties can be obtained by setting it as 0.5 equivalent - 1.5 equivalent.

When the hardening reaction is performed using the hardening agent, a hardening accelerator may be used in combination. Examples of usable curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; Aminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7 and other tertiary amines; triphenylphosphine, diphenylphosphine , tributylphosphine and other organic phosphines; metal compounds such as tin octoate; tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate and other tetrasubstituted phosphonium-tetrasubstituted borates; 2 -Ethyl-4-methylimidazole-tetraphenyl borate, N-methylmorpholine-tetraphenyl borate and other tetraphenyl boron salts; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid Carboxylic acid compounds such as dicarboxylic acid, naphthoic acid, and salicylic acid, etc. From the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin, carboxylic acid compounds such as salicylic acid are preferred. The hardening accelerator can be used as needed in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.

Furthermore, an inorganic filler can be added to the epoxy resin composition of this invention as needed. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite , steatite, spinel, titanium dioxide, talc, and other powders, or beads obtained by spheroidizing these, but are not limited to these. These may be used alone, or two or more kinds may be used. The amount of these inorganic fillers differs depending on the application. For example, when used as a sealant for semiconductors, the heat resistance, moisture resistance, mechanical properties, and flame retardancy of the cured epoxy resin composition In terms of other aspects, it is preferable to use it in a proportion of more than 20% by weight in the epoxy resin composition, more preferably more than 30% by weight, especially in order to increase the linear expansion rate relative to the lead frame, and more preferably It is used in a proportion of 70% to 95% by weight.

In the epoxy resin composition of the present invention, a mold release agent may be blended in order to facilitate mold release from the mold during molding. As the release agent, any of the previously known ones can be used, for example, ester waxes such as carnauba wax and montan wax; fatty acids such as stearic acid and palmitic acid, and metal salts thereof ; Polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene. These may be used alone or in combination of two or more. It is preferable that the compounding quantity of these release agents is 0.5 weight% - 3 weight% with respect to all organic components. If the amount is too small, the release from the mold will deteriorate, and if the amount is too large, the adhesion to the lead frame and the like will deteriorate.

In the epoxy resin composition of the present invention, in order to improve the adhesion between the inorganic filler and the resin component, a coupling agent can be formulated. As the coupling agent, any of the previously known ones can be used, for example, vinyl alkoxysilane, epoxy alkoxysilane, styryl alkoxysilane, methacryloxyalkoxysilane , acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxysilane and other alkoxysilane compounds, alkoxytitanium compounds, aluminum chelates Wait. These may be used alone or in combination of two or more. Regarding the method of adding the coupling agent, the surface of the inorganic filler can be pre-treated with the coupling agent and then kneaded with the resin, or the inorganic filler can be kneaded after mixing the coupling agent in the resin.

Furthermore, in the epoxy resin composition of this invention, a well-known additive can be mix|blended as needed. Specific examples of additives that can be used include: polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and Imide-based compounds, cyanate-based compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The epoxy resin composition of the present invention can be easily produced into its cured product by the same method as the conventionally known method. For example, by sufficiently mixing epoxy resin with hardener, and hardening accelerator, inorganic filler, release agent, silane coupling agent, and additives as needed to uniformity using extruder, kneader, roll, etc. as needed, Obtain the epoxy resin composition of the present invention, mold it by melt casting method or transfer molding method, injection molding method, compression molding method, etc., and then heat at 80°C to 200°C for 2 hours to 10 hours, whereby it can be Get hardened.

Moreover, the epoxy resin composition of this invention may contain a solvent as needed. Impregnate an epoxy resin composition (epoxy resin varnish) containing a solvent into a fibrous material (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heat and dry it. A prepreg is obtained, and the obtained prepreg is thermocompressed to produce a cured product of the epoxy resin composition of the present invention. The solvent content of the epoxy resin composition is usually 10% by weight to 70% by weight, preferably about 15% by weight to 70% by weight, based on the internal ratio. Examples of solvents include: γ-butyrolactones; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl Amide-based solvents such as imidazolidinone; Tetramethylene glycol and other solvents; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl Ether-based solvents such as ether, preferably mono- or di-lower (1-3) alkyl ethers of lower (1-3 carbon number) alkanediols; ketones such as methyl ethyl ketone and methyl isobutyl ketone A solvent, more preferably a di-lower (1-3 carbon number) alkyl ketone whose two alkyl groups may be the same or different; aromatic solvents such as toluene and xylene, and the like. These may be used alone, or may be a mixed solvent of two or more.

In addition, a sheet-shaped adhesive agent (sheet of the present invention) can be obtained by applying the above-mentioned epoxy resin varnish on a release film, removing the solvent under heating, and performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The cured product obtained in the present invention can be used in various applications. Specifically, general applications using thermosetting resins such as epoxy resins are listed, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printing Substrates, wire coverings, etc.), sealants, and other additives to other resins, etc.

Examples of the adhesive include those for civil engineering, construction, automobiles, general office work, medical treatment, and other electronic materials. Among these, adhesives for electronic materials include: interlayer adhesives for multilayer substrates such as build-up substrates; adhesives for semiconductors such as die bonding agents and underfills; ball grid arrays (BGA) Underfill for reinforcement, anisotropic conductive film (ACF), anisotropic conductive paste (ACP) and other mounting adhesives.

Examples of the sealant include potting, dipping, and transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, and large scale integration circuits (LSI); Used for potting and sealing of chip on board (COB), chip on film (COF), tape automated bonding (TAB), etc. of IC and LSI; Underfill for crystals; sealing for IC packages such as quad flat package (QFP), ball grid array (BGA), and chip size package (CSP) during installation (including underfill for reinforcement) Wait. [Example]

Next, the present invention will be described more specifically by way of examples, and unless otherwise specified, parts are parts by weight. In addition, this invention is not limited to these Examples. In addition, in the examples, the epoxy equivalent was measured by a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K-7236, and the softening point was measured by a method based on JIS K-7234.

･GPC (gel permeation chromatography) analysis Column: SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 0.5ml/min. Column temperature: 40°C Solvent used: THF (tetrahydrofuran) Detector: RI (Differential Refractive Detector)

[Synthesis Example 1] Add 100 parts of toluene, 84 parts of dicyclopentadiene-type phenol resin (hydroxyl equivalent: 168 g/eq.), 58.0 parts of indene, and 5 parts of methanesulfonic acid, heat up to 125° C., and react for 6 hours. After adding 150 parts of toluene, the organic layer was washed with water until the waste liquid became neutral, and then concentrated to obtain 115 parts of phenol resin (P1). The number average molecular weight Mn: 686, the weight average molecular weight Mw: 854, the hydroxyl equivalent is 284.2 g/eq. The GPC profile is shown in FIG. 1 .

[Example 1] While carrying out nitrogen purging to the flask equipped with thermometer, cooling pipe, fractionating pipe and stirrer, add 110 parts of phenol resin (P1) obtained in Example 1, 143 parts of epichlorohydrin, 35.8 parts of dimethyl sulfide, 1.4 parts of water, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 45° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 150 parts of MIBK was added, and the organic layer was washed once with 100 parts of water. Put the organic layer back into the reaction container, add 15 parts of 30 wt% sodium hydroxide aqueous solution, and react at 70° C. for 2 hours. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain 123 parts of the target compound (E1) as a brown solid resin. The number average molecular weight Mn: 723, the weight average molecular weight Mw: 953, the epoxy equivalent is 360.5 g/eq., the ICI viscosity (150°C) is 1.07 Pa·s, and the softening point is 95.2°C. The GPC profile is shown in FIG. 2 .

[Synthesis Example 2] Add 84 parts of dicyclopentadiene-type phenol resin (hydroxyl equivalent: 168 g/eq.), 54.2 parts of benzyl alcohol, and 1.4 parts of p-toluenesulfonic acid monohydrate, and heat up to 150°C while distilling off the generated water. React for 3 hours. 100 parts of toluene was added, and the organic layer was washed with water until the waste liquid became neutral, and then concentrated to obtain 95 parts of phenol resin (P2). The number average molecular weight Mn: 699, the weight average molecular weight Mw: 769, the hydroxyl equivalent is 258.1 g/eq. The GPC profile is shown in FIG. 3 .

[Synthesis Example 3] While carrying out nitrogen purging to the flask equipped with a thermometer, a cooling pipe, a fractionating pipe, and a stirrer, 80 parts of phenol resin (P2), 115 parts of epichlorohydrin, 28.7 parts of dimethylsulfoxide, and 1.3 parts of water, and the internal temperature was raised to 45°C. After adding 12.8 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 45° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 146 parts of MIBK were added, and the organic layer was washed once with 100 parts of water. Put the organic layer back into the reaction container, add 15 parts of 30 wt% sodium hydroxide aqueous solution, and react at 70° C. for 2 hours. After standing to cool, the organic layer was washed three times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain the target compound (E2) as a brown solid resin. The number average molecular weight Mn: 698, the weight average molecular weight Mw: 824, the epoxy equivalent is 332.1 g/eq., the ICI viscosity (150°C) is 0.08 Pa·s, and the softening point is 59.8°C. The GPC profile is shown in FIG. 4 .

[Example 2, Comparative Example 1 to Comparative Example 3] Use the epoxy resin (E1) obtained in Example 1, the epoxy resin (E2) obtained in Synthesis Example 3, and bisphenol F-type epoxy resin (RE-304S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 169 g/eq.), epoxy resin derived from dicyclopentadiene type phenolic resin (XD-1000-2L, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 238 g/eq., ICI viscosity (150°C): 0.05, softening point: 55.4°C), and 4,4'-methylenebis(2,6-diethylaniline) as a hardening agent (manufactured by Nippon Kayaku Co., Ltd., Kayabond (KAYABOND) C-300S ), and prepared in the ratio (parts by weight) in Table 1, uniformly mixed/kneaded with a mixing roller, and then released from the mold, hardened under the conditions of 2 hours at 160°C and 6 hours at 180°C to obtain evaluation Use a test piece.

＜Measurement of hardened physical properties＞ Table 1 shows the results obtained by measuring the test pieces for evaluation under the following conditions.

＜Heat Resistance Test＞ The glass transition temperature (the temperature at which tan δ becomes the maximum value) was measured using a dynamic viscoelasticity testing machine. ･Dynamic viscoelasticity measuring device: DMA-2980 manufactured by TA-instruments ･Heating rate: 2°C/min

＜Bending coefficient of elasticity＞ Measurement was performed in accordance with JIS K-6911. ･Tensilon: RTG-1310 (manufactured by A&D Company, Limited) ･Measurement temperature: room temperature

＜Water Absorption＞ Calculated from the mass change after holding a disk-shaped test piece having a diameter of 5 cm×a thickness of 4 mm under 100° C. water immersion conditions for 24 hours.

[Table 1] Example 2 Comparative example 1 Comparative example 2 Comparative example 3 epoxy resin E1 100 E2 100 XD-1000-2L 100 RE-304S 100 hardener KAYABOND C-300S twenty two twenty three 33 46 Evaluation results Tg(DMA) ℃ 174 145 201 155 Bending modulus of elasticity (30°C) GPa 2.9 2.8 2.3 2.3 Water absorption (100℃/100%) % 0.55 0.69 0.82 1.2

From the results in Table 1, it was confirmed that Example 2 has high heat resistance, high modulus of elasticity, and low water absorption. [Industrial availability]

The epoxy resin of the present invention can be effectively used as insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, substrates for BGA, build-up substrates, etc.), adhesives (conductive adhesives) etc.) or various composite materials represented by CFRP, coatings, etc., especially, it can be effectively used for various composite materials represented by CFRP that strongly requires a high modulus of elasticity.

none

FIG. 1 shows a GPC chart of Synthesis Example 1. FIG. 2 shows the GPC chart of Example 1. FIG. 3 shows a GPC chart of Synthesis Example 2. FIG. 4 shows a GPC chart of Synthesis Example 3.

Claims (7)

An epoxy resin represented by the following formula (1),

In formula (1), n is the number of repetitions, and its average value is 1<n<20; R represents the substituent represented by the following formula (2); p represents real numbers from 0 to 4, and the average value of p is 0.5 ~1.5,

In formula (2), * represents a bonding part with the aromatic ring of formula (1); X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons; and q represents a real number of 0 to 5. An epoxy resin represented by the following formula (3),

In formula (3), n is the number of repetitions, and its average value is 1<n<20. The epoxy resin according to Claim 1 or Claim 2, wherein the weight average molecular weight obtained by gel permeation chromatography (GPC) is 400-3000. A curable resin composition containing the epoxy resin according to any one of claim 1 to claim 3. The curable resin composition according to claim 4 further contains an amine-based curing agent. A cured product obtained by curing the curable resin composition described in Claim 4 or Claim 5. A method for producing an epoxy resin, which is the method for producing an epoxy resin as described in any one of claim 1 to claim 3, comprising: making the polycondensate of a dicyclopentadiene compound and a phenolic compound and indene a step of reacting derivatives to obtain a phenol resin; and a step of epoxidizing the phenol resin.

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