WO2008047613A1

WO2008047613A1 - Epoxy resin, method for producing the epoxy resin, epoxy resin composition using the epoxy resin, and cured product of the epoxy resin composition

Info

Publication number: WO2008047613A1
Application number: PCT/JP2007/069494
Authority: WO
Inventors: Koichi Kawai; Katsuhiko Oshimi; Takao Sunaga; Masataka Nakanishi
Original assignee: Nipponkayaku Kabushikikaisha
Priority date: 2006-10-11
Filing date: 2007-10-04
Publication date: 2008-04-24
Also published as: JP5319289B2; TW200817450A; TWI414536B; JPWO2008047613A1

Abstract

Disclosed is an epoxy resin which is obtained by epoxidizing a phenol resin represented by the formula (1) below and having a hydroxyl equivalent of 160-230 g/eq. (1) (In the formula, P, R and m are independent from one another, and P represents an alkyl group having 1-6 carbon atoms, R represents a hydrogen or an alkyl group having 1-6 carbon atoms, and m represents an integer of 0-3. In this connection, n represents the number of repetitions.) The epoxy resin is capable of providing a cured product which is excellent in low water absorption, low dielectric property, flame retardance and heat resistance. Also disclosed are an epoxy resin composition containing the epoxy resin and a curing agent and a cured product obtained by curing the epoxy resin composition.

Description

Specification

Epoxy resin and production method thereof, and epoxy resin composition and cured product using the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin, a method for producing the same, an epoxy resin composition containing the epoxy resin, and a cured product of the epoxy resin composition, and more particularly to a cured product having low water absorption and low dielectric properties. It relates to an epoxy resin that can be provided. Background art

[0002] Epoxy resins are cured with various curing agents, and generally become cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. It is used in a wide range of fields such as plates, molding materials, casting materials, and resists.

[0003] In recent years, with the rapid development of electrical and electronic equipment, the density and integration of electrical and electronic parts have been rapidly advanced. For example, lead-free solder heat-resistant materials are required for package materials, and excellent heat resistance and water absorption are desired for the cured products.

[0004] In addition, a material used for a substrate, particularly a substrate laminated at a high density, is required to have excellent electrical insulation, and its cured product is required to have low dielectric properties.

[0005] In addition, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants for electrical and electronic parts. Products using these materials are treated with toxic substances such as dioxin by inappropriate treatment after disposal. It has been pointed out that it contributes to the occurrence. As one method for solving the above problem, an epoxy resin having a phosphorus atom in the skeleton has been proposed. In particular, even if ordinary phosphoric acid ester type compounds are not used, those having excellent flame retardancy compared to conventional epoxy resins have been developed by selecting a resin skeleton. At present, a search for a resin skeleton that expresses flame retardancy without using a flame retardant, particularly called “halogen-free and phosphorus-free” is being conducted.

[0006] Examples of flame retardant epoxy resins that satisfy these requirements include phenol aralkyl epoxy resins, but they have not been able to meet the recent high performance requirements and are expected to further improve their properties. Talk to me. (Japanese Unexamined Patent Publication No. 2006-063207 and Japanese Unexamined Patent Publication No. 2001-172473 See No. Gazette. )

Disclosure of the invention

[0007] Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide an epoxy resin that is excellent in flame retardancy and heat resistance, and can provide a cured product having low water absorption and low dielectric properties. And a manufacturing method thereof. Another object of the present invention is to provide an epoxy resin composition containing such an epoxy resin and a cured product thereof.

[0008] As a result of intensive studies in view of the above-described actual situation, the present inventors have found that by using a modified epoxy resin having a skeleton derived from 1,3-alkyl-substituted benzene, such as a xylene skeleton, low water absorption, The inventors have found that a cured product excellent in low dielectric property, flame retardancy and heat resistance can be obtained, and completed the present invention.

That is, the gist configuration of the present invention is as follows.

[0010] 1. Formula (1) below:

(Wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 3) Wherein n is the number of repetitions), and is obtained by epoxidizing a phenol resin having a hydroxyl group equivalent of 160 to 230 g / eq. .

[0011] 2. An epoxy resin composition comprising the epoxy resin according to 1 above and a curing agent.

[0012] 3. A cured product obtained by curing the epoxy resin composition described in 2 above.

[0013] 4. Formula (1) below:

(Wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 0 to 3. N is the number of repetitions. And a phenolic resin having a hydroxyl group equivalent of 160 to 230 g / eq is reacted with an epihalohydrin.

According to the present invention, an epoxy resin capable of providing a cured product having low water absorption and low dielectric properties by epoxidizing a phenol resin having a skeleton derived from 1,3-alkyl-substituted benzene, and A manufacturing method thereof can be provided. In addition, Epoxy resin compositions containing such epoxy resins, useful for a wide range of applications such as electrical / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, and resist applications, and cured products thereof are provided. It ’s the power to do.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The epoxy resin of the present invention has the following formula (1):

(Wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 3) N is the number of repetitions), and the phenolic resin having a hydroxyl equivalent weight of 160 to 230 g / eq is reacted with, for example, epihalohydrin in the presence of an alkali metal. It is obtained by epoxy.

[0016] In the formula (1), P is an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a propyl group, a pentyl group, a hexyl group, a cyclohexyl group, and among these, a methyl group is particularly preferable. R is a hydrogen atom or an alkyl group having from 6 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a propyl group, a pentyl group, a hexyl group, a cyclohexyl group, and the like. Most preferred R is a hydrogen atom. Further In addition, the repeating number n is usually an integer of 1 to 40, preferably an integer of 1 to 20, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 2.

[0017] The phenol resin represented by the formula (1) is, for example, an acid comprising 1,3-alkyl-substituted benzene (m-xylene, 1-methyl-3-ethylbenzene, 1,3-jetylbenzene, etc.) and formaldehyde. After reacting with a catalyst (an inorganic strong acid such as sulfuric acid or nitric acid, an organic sulfonic acid such as p-toluenesulfonic acid or xylene sulfonic acid, or an organic acid such as oxalic acid), phenols (phenol or alkyl-substituted phenol) Can be synthesized by reacting with. The phenol resin that can be used as a raw material in the present invention, if the phenol resin represented by the above formula (1) is a main component, other aromatic aldehyde resin by-produced in the process of synthesizing the resin. As a mixture of these which may be contained, those having a hydroxyl group equivalent of 160 to 230 g / eq and preferably 180 to 210 g / eq are preferable. Further, n in the above formula (1) usually represents an integer of !!-40.

[0018] An example of the method for synthesizing the epoxy resin of the present invention will be described below. The epoxy resin of the present invention uses a phenol resin represented by the above formula (1) and reacts with epihalohydrin.

Examples of the epihalohydrin used in the epoxidation reaction include epichlorohydrin, α_methyl epipic hydrin, γ-methyl epichlorohydrin, epip mouth hydrin and the like in the present invention. Is preferably epichlorohydrin, which is easily available industrially. The amount of epihalohydrin used is usually 2 to 20 mol, preferably 4 to 10 mol, per 1 mol of the hydroxyl group of the phenol resin represented by the above formula (1).

[0020] In the epoxidation reaction, an alkali metal hydroxide is preferably used.

Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Note that the alkali metal hydroxide may be used as a solid or an aqueous solution thereof. For example, when an alkali metal hydroxide is used as an aqueous solution, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or normal pressure. The epoxidation reaction can be carried out by removing the water by liquid separation, removing the water, and continuously returning the epihalohydrin to the reaction system. The amount of alkali metal hydroxide used is the phenol tree represented by the above formula (1). It is usually 0.9 to 3.0 mol, preferably 1.0 to 2.0 mol, and more preferably (1.0 to 1.5 monole to 1 mol of the hydroxyl group of fat.

[0021] In the epoxidation reaction, a quaternary ammonium salt such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethylbenzyl ammonium chloride or the like may be added as a catalyst to accelerate the reaction. I like it. The amount of the quaternary ammonium salt used is usually 0.1 to 5 g, preferably 0.2 to 0 g, per 1 mol of the hydroxyl group of the phenol resin represented by the above formula (1).

[0022] In the above epoxidation reaction, the reaction is further carried out by adding an alcohol such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran or dioxane. Is preferable for the progress of the reaction.

[0023] When the above alcohols are used, the amount used is usually 2 to 50% by mass, preferably 4 to 20% by mass, based on the amount of epihalohydrin used. On the other hand, when an aprotic polar solvent is used, the amount thereof used is usually 5 to 100% by mass, preferably 10 to 80% by mass, based on the amount of epihalohydrin used.

[0024] In the epoxidation reaction, the reaction temperature is usually 30 to 90 ° C, preferably 35 to

80 ° C. On the other hand, the reaction time is usually 0.5 to 10 hours, preferably;! To 8 hours. The reaction product of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, or the like under heating and reduced pressure after washing with water or without washing with water. In order to make epoxy resin with less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. Thus, the ring-closing reaction of the by-product can be carried out to ensure the ring-closing of the by-products, no and rhohydrin. In this case, the amount of the alkali metal hydroxide used is usually from 0.01 to 0.3 monolayer of the hydroxyl group 1 monolayer of the phenol resin represented by the above formula (1) used for the epoxidation. (A 0.05-0.2 monolayer. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

[0025] In the epoxidation reaction, after the completion of the reaction, the generated salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention. I can do it. The epoxy resin of the present invention is an epoxy resin obtained by epoxidizing (glycidylating) a phenol resin mainly composed of a phenol resin represented by the above formula (1) by using epichlorohydrin as an epihalohydrin. Specifically, the resin is preferred: Formula (2) below:

(Wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 3) In addition, n is a repeating number, and usually represents an integer of 1 to 40, and G represents a glycidyl group.) It is preferably an epoxy resin mainly composed of an epoxy resin represented by . In the formula (2), P, R and m are as described for P, R and m in the formula (1).

[0026] The epoxy resin of the present invention can be used as a raw material for various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds, and cyclic carbonate compounds.

[0027] The epoxy resin composition of the present invention will be described below. The epoxy resin composition of the present invention is required to contain the above-described epoxy resin of the present invention and a curing agent as essential components. In the epoxy resin composition of the present invention, the above-described epoxy resin of the present invention can be used alone, or the epoxy resin of the present invention can be used in combination with other epoxy resins. When the epoxy resin of the present invention is used in combination with other epoxy resins, the content of the epoxy resin of the present invention in the entire epoxy resin is preferably 30% by mass or more, particularly preferably 40% by mass or more. However, when the epoxy resin of the present invention is used as a modifier in the epoxy resin composition of the present invention, the content power of the epoxy resin of the present invention occupies the entire epoxy resin; Is preferred.

[0028] Other epoxy resins that can be used in combination with the epoxy resin of the present invention include, for example, nopolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, Examples include phenylmethane type epoxy resins and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3, 3 ,, 5, 5, 1 Tetramethyl mono [1,1,1biphenyl] —4,4,1diol, Hyde mouth quinone, resorcin, naphthalenediol, tris (4-hydroxyphenenole) methane, 1,1,2,2,2 tetrakis (4hydroxy) Phenylol) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetoaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyl Acetofenone, o hydroxy Cetophenone, dicyclopentagen, furfural, 4,4'bis (chloromethyl) 1,1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1,1'-biphenyl, 1,4bis (chloromethinole) ) Polycondensates with benzene, 1,4 bis (methoxymethinole) benzene, etc., and their modified products, halogenated bisphenols such as tetrabromobisphenol A, alcohols, glycidyl ether derivatives derived from alcohols, alicyclic rings Forces including solid or liquid epoxy resins such as formula epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins and the like are not limited to these. These resins may be used alone or in combination of two or more.

Examples of the curing agent contained in the epoxy resin composition of the present invention include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. Specific examples of the curing agent that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, and isophoronediamine; dimer of dicyandiamide and linolenic acid, and ethylenediamine. Amide compounds such as polyamide resin synthesized; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride Acid, acid anhydride compounds such as methylhexahydrophthalic anhydride; bisphenols such as bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, tetrabromobisphenol A, etc. Terpene diphenol, 4, 4'-biphenol, 2, 2, monobiphenol, 3, 3, , 5, 5, monotetramethyl [1,1,1'-biphenyl] —4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris (4hydroxyphenenole) methane, 1,1, Polyhydric phenolic compounds such as 2,2-tetrakis (4-hydroxyphenyl) ethane; phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetoaldehyde , Benzaldehyde, ρ-hydroxybenzaldehyde, ο-hydroxybenzaldehyde, ρ-hydroxyacetophenone, ο-hydroxyacetophenone, dicyclopentagen, polyphenols with phenol and their modified products; the above phenols And 4, 4 'Bis (methyl methyl) 1, 1' — Biphenyl, 4, 4'-bis (methoxymethyl) -1,1,1'-biphenyl, 1,4, monobis (chloromethyl) benzene, 1,4, monobis (methoxymethyl) benzene and other polycondensates And the like, and other modified compounds, imidazoles, trifluoroborane amine complexes, guanidine derivatives, condensates of terpenes and phenols, etc. A phenol aralkyl resin having the following skeleton is preferred. These curing agents may be used alone or in combination of two or more.

[0030] The content of the curing agent in the epoxy resin composition of the present invention is based on 1 equivalent of the epoxy group of the entire epoxy resin (the epoxy resin of the present invention and other epoxy resins, the same shall apply hereinafter). 0.7 to 1; 1.2 equivalents are preferred. If the content of the curing agent is less than 0.7 equivalents or more than 1.2 equivalents relative to 1 equivalent of epoxy group, curing of the epoxy resin composition will be incomplete in any case and good. Hardened physical properties may not be obtained.

[0031] The epoxy resin composition of the present invention may further contain a curing accelerator. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2 (dimethinoreaminomethinole) phenol, 1,8 diazabicyclo (5, 4 , 0) tertiary amines such as undecene 7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The content of the curing accelerator is appropriately selected as necessary, but is 0.;! To 5. with respect to 100 parts by mass of the total epoxy resin (the epoxy resin of the present invention and other epoxy resins, the same shall apply hereinafter). It is preferably 0 parts by mass. [0032] The epoxy resin composition of the present invention may contain a binder resin as necessary. Nonder resins include petrol-based resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR (acrylonitrile-butadiene rubber) monophenol resins, epoxy NBR resins, polyamide resins, polyimide resins. The force includes, for example, a silicone-based resin, but is not limited thereto. The content of the binder resin is appropriately selected as necessary, but the epoxy resin composition preferably has a range that does not impair the flame retardancy and heat resistance. On the other hand, it is usually 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass.

[0033] In addition, the epoxy resin composition of the present invention can be added with an inorganic filler as required. As inorganic fillers, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zircoure, phosphorite, steatite, spinel, titania, talc, etc. Alternatively, the force includes, for example, beads obtained by spheroidizing these, but is not limited thereto. These inorganic fillers may be used alone or in combination of two or more. The content of these inorganic fillers is preferably 0 to 95% by mass in the epoxy resin composition of the present invention, but 50 to 95% by mass is more preferable from the viewpoint of flame retardancy and mechanical strength. -95% by weight is particularly preferred. Furthermore, the epoxy resin composition of the present invention includes a silane coupling agent, a release agent such as stearic acid, normitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins. Can be added.

[0034] The epoxy resin composition of the present invention comprises the epoxy resin of the present invention, a curing agent, and various components appropriately selected as necessary, using an extruder, a kneader, a roll, or the like as necessary. Can be obtained by mixing together. Moreover, the cured product of the epoxy resin composition of the present invention can be easily obtained by curing the epoxy resin composition by a method similar to a conventionally known method. Specifically, for example, the epoxy resin of the present invention, a curing agent, and various components appropriately selected as necessary (a curing accelerator, an inorganic filler, etc.), an extruder, a kneader, a roll as necessary. Mix well until uniform to obtain an epoxy resin composition, melt the epoxy resin composition, mold using a casting or transfer molding machine, etc., and further 80-200 ° By heating at C for 2-10 hours, A cured product of the epoxy resin composition of the present invention can be obtained.

[0035] Further, the cured product of the epoxy resin composition of the present invention is obtained by converting the above-described epoxy resin composition into toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethinoformamide, dimethylacetamide, N-methyl. Dissolve in a solvent such as pyrrolidone to make an epoxy resin composition varnish, then impregnate the varnish into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and heat dry. The obtained prepredder can be obtained by hot press molding. The amount of the solvent used for the varnish of the epoxy resin composition is usually 10 to 70% by mass, preferably 15 to 70% by mass, in the mixture of the epoxy resin composition and the solvent. is there.

[0036] When the epoxy resin of the present invention is used as a modifier for a film-type epoxy resin composition, specifically, flexibility and the like in the B-stage can be improved. Such a film-type epoxy resin composition can be obtained as a sheet-like adhesive by, for example, applying the varnish of the above-described epoxy resin composition on a release film and removing the solvent under heating. This sheet-like adhesive can be used as an interlayer insulation layer in multilayer substrates.

[0037] The epoxy resin composition and the cured product thereof of the present invention can be used for various applications such as adhesives and sealants. Examples of the adhesive include civil engineering, architectural, automotive, general office and medical adhesives, and electronic material adhesives. In addition, as adhesives for electronic materials, specifically, interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive materials Adhesive for mounting such as conductive film (ACF) and anisotropic conductive paste (ACP).

[0038] Further, as the sealing material, potting, dating, transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., ICs, LSI type COBs, COFs, TABs, etc. Examples include potting sealing, underfill used for flip chips, sealing when mounting IC packages such as BGA and CSP (reinforcing underfill).

<0039><Example> Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the following, unless otherwise specified, “parts” in the composition display means parts by mass. Moreover, the epoxy equivalent and the softening point were measured by the following methods.

[0040] (1) Epoxy equivalent

It was measured by the method described in JIS K-7236. The unit is g / eq.

[0041] (2) Softening point

It was measured by the method described in JIS K-7234. Units. C.

[0042] (Reference Synthesis Example 1)

According to the method described in JP 2004-277717 A, the following formula (b):

(Where n is about 3 (average value).) Epoxy of phenol aralkyl resin (XLC-3L, manufactured by Mitsui Chemicals, OH equivalent 172g / eq, softening point 71 ° C) Made. Specifically, in a flask equipped with a stirrer, a reflux condenser, and a stirrer, add 100 parts of XLC-3L and 268 parts of epichloronohydrin, raise the temperature to 120 ° C, dissolve, and dissolve this solution. Into this, 58 parts of 40 mass% sodium hydroxide aqueous solution was gradually added dropwise over 3 hours. During the addition, water azeotroped was discharged out of the system by a Dean-Stark water separator, and epichlorhydrin was reacted while returning to the system. The reaction temperature was kept at 100 to 115 ° C. After completion of the dropwise addition, the mixture was further refluxed and aged at 115 ° C to 120 ° C for an additional hour after the water was no longer distilled to complete the reaction. Next, the reaction solution is cooled to room temperature, and the formed salt is removed by filtration, and then epichlorohydrin is distilled off under the conditions of heating and decompression at a maximum of 140 ° C. to obtain the above formula (b) An epoxidized phenol aralkyl resin represented by the formula (crude) was obtained. The crude phenol aralkyl epoxidized product thus obtained was dissolved in 406 parts of methyl isobutyl ketone to obtain a uniform solution. To this solution was added 290 parts of 2% aqueous sodium hydrogen phosphate solution, and the mixture was stirred at 50 ° C for 2 hours. Rinse with pure water 3 times. Methyl isobutyl ketone was distilled off under heating and depressurization conditions up to 150 ° C. 130 parts of an epoxidized phenol aralkyl resin (epoxy resin (b)) purified as a residue was obtained. The epoxy equivalent of the obtained epoxy resin (b) was 238 g / eq, and the softening point was 52.0 ° C.

[0044] (Example 1)

A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen while the following formula (3):

(Wherein, n represents the number of repetitions) 100 parts of xylene formaldehyde resin (Zyster GP90, manufactured by Fudou Co., Ltd., OH equivalent 197 g / eq, softening point 85 ° C), 187 parts of epichlorohydrin, and methanol Add 11 parts, raise the temperature to 75 ° C with stirring, dissolve, add 21 parts of flaky sodium hydroxide in 90 minutes, and then keep the temperature at 75 ° C 1. The reaction was carried out for 25 hours. After completion of the reaction, washing with water was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 144 ° C. using a rotary evaporator. The residue was dissolved by adding 242 parts of methylisobutyl ketone and heated to 70 ° C. After stirring, 8 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was subjected to 180 ° using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure with C, 126 parts of the epoxy resin (a) of the present invention was obtained. The epoxy resin (a) obtained had an epoxy equivalent of 279 g / eq and a softening point of 65.0 ° C.

[0045] (Example 2 and Comparative Example 1)

Epoxy resin (a) obtained in Example 1, epoxy resin (b) obtained in Reference Synthesis Example 1 as a comparative example, KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., OH equivalent 199 g / eq, Softening point 65. 0 ° C, Bifuran roof enol condensation type phenol aralkyl resin), and TPP (Triphenylphosphine, Hokuko Chemical Co., Ltd.) as curing accelerator Epoxy resin compositions for comparison with the present invention were prepared with the formulation (parts by mass) shown in Table 1 using a formula company. The epoxy resin composition was formed into a resin molding by transfer molding (175 ° C, 60 seconds), and further cured at 160 ° C for 2 hours and further at 180 ° C for 8 hours.

[0046] One

[0047] The water absorption and dielectric constant of the cured product thus obtained were measured by the following methods. The results are shown in Table 2.

[0048] (3) Water absorption test

The cured product is a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm, and ( _a ) the weight increase rate (%) after boiling for 24 hours in 100 ° C water, and (b) 85 ° C, Weight increase rate (%) after immersion for 24 hours under conditions of 85% relative humidity, and (c) Weight increase rate (%) after immersion for 24 hours under conditions of 121 ° C and 100% relative humidity Asked.

[0049] (4) Dielectric constant measurement

A dielectric constant was measured using a 1 GHz cavity resonator (manufactured by Kanto Electronics Development Co., Ltd.) as a dielectric loss tangent measurement jig.

[0050] Table 2

(Example 3 and Comparative Example 2)

Epoxy resin (a) obtained in Example 1, epoxy resin (b) obtained in Reference Synthesis Example 1 as a comparative example, KAYAHARD GPH-65 as a curing agent, TPP as a curing accelerator, none Table 3 uses MSR—2212 (manufactured by Tatsumori Co., Ltd.) as the filler, Carnava No. 1 (manufactured by Celerica NODA) as the wax, and KBM—303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the coupling agent. The epoxy resin composition for this invention and a comparison was prepared with the mixing | blending prescription (mass part) shown. The epoxy resin composition was formed into a resin molded body by transfer molding (175 ° C, 60 seconds), and further cured at 160 ° C for 2 hours and further at 180 ° C for 8 hours.

[0052] Table ₃

[0053] The flame retardancy of the cured product thus obtained was measured by the following method. The results are shown in Table 4.

[0054] (5) Flame retardancy

In accordance with UL-94, the total burning time was measured for specimens with a thickness of 0.8 mm and 1.6 mm. The total combustion time is the time until self-extinguishing.

[0055]

Table 4

[0056] (Example 4)

Epoxy resin (a) obtained in Example 1, xylene formaldehyde resin represented by the above formula (3) as a curing agent (Zyster GP90, manufactured by Fudou Co., Ltd., OH equivalent 197 g / eq, softening point 85 ° C), And TPP as a curing accelerator, with the formulation (parts by mass) shown in Table 5. The epoxy resin composition of the present invention was prepared. The epoxy resin composition was formed into a resin molding by transfer molding (175 ° C., 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 5

[0058] The water absorption and dielectric constant of the cured product thus obtained were measured in the same manner as in Example 2.

. The results are shown in Table 6.

[0059] Table 6

[0060] The cured product of the epoxy resin composition of the present invention has a low water absorption and a low dielectric property as shown in Table 2, compared with the cured product of the epoxy resin composition of the comparative example. As shown in Table 4, it can be seen that it is a cured product with flame retardancy with a short burning time. Furthermore, from the results in Table 6, an epoxy resin composition containing a phenol aralkyl resin having the same main skeleton as the epoxy resin of the present invention as a curing agent has a further low water absorption and low dielectric constant in the cured product. It is clear that sex can be imparted.

[0061] The epoxy resin composition and the cured product thereof of the present invention are useful in the field of electrical and electronic materials, particularly in semiconductor encapsulation and substrates, by taking advantage of these characteristics.

Claims

The scope of the claims

[1] Formula (1) below:

[2] An epoxy resin composition comprising the epoxy resin according to claim 1 and a curing agent.

[3] A cured product obtained by curing the epoxy resin composition according to claim 2.

[4] Formula (1) below:

(Wherein P, R and m are each independently present, P is an alkyl group having 1 to 6 carbon atoms, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 3) And n is the number of repetitions.) An epoxy resin characterized by reacting a phenol resin having a hydroxyl group equivalent of 160 to 230 g / eq with epihalohydrin. Manufacturing method.