JP5153081B2 - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin having a high molecular orientation and an epoxy resin, an epoxy resin composition and a cured product thereof having excellent properties of toughness and moisture resistance in the cured product.

  In general, it is known that an epoxy resin composition forms a random network structure by a crosslinking reaction and becomes a cured product excellent in heat resistance, water resistance, insulation and the like. Furthermore, in recent years, when an epoxy resin composition is cured, an attempt has been made to improve the properties of the cured product by applying an external physical force to orient the epoxy resin composition in a specific direction. For example, Patent Document 1 describes that an epoxy resin having a mesogenic group in the molecule exhibits high thermal conductivity in the cured product. In Patent Document 2, it is reported that a cured product having excellent thermal conductivity can be obtained by applying a magnetic field to an epoxy resin having a mesogenic group and then curing it. Further, in the field of thermoplastic resins, Patent Document 3 describes that a polymer having liquid crystallinity can be processed at a temperature equal to or higher than the melting point to obtain a molded product having excellent mechanical strength.

JP 2003-268070 A JP 2004-175926 A Japanese Patent No. 2664405

  However, an epoxy resin having a mesogenic group as described in the above-mentioned patent document generally has a drawback that it has a complicated molecular structure and is difficult to produce. Moreover, when applying a magnetic field etc. to the whole epoxy resin composition, there exists a problem that a large apparatus is needed. In general, a thermoplastic liquid crystal polymer has a melting point of 250 to 350 ° C., and the molding conditions are generally very strict as compared with a thermosetting resin.

  In light of these circumstances, the present inventors have eagerly studied for an epoxy resin composition that is easy to manufacture and that can easily realize a state in which molecules are oriented. As a result, the present invention has been completed. It was.

（式中、複数存在するＲは独立して水素原子もしくはフェニル基を表す。複数存在する基

は、炭素数ａ個の置換または非置換のシクロアルキル基を表し、それぞれ互いに同一であっても異なっていてもよい。ａは３〜１７（アルキリデン結合の炭素を含む）を表す。ｎは平均値であり０．５＜ｎ≦２０を表す。）
で表されるエポキシ樹脂、
（２）下記式（１’）

（式中、複数存在するＲは独立して水素原子もしくはフェニル基を表す。複数存在する基

は、それぞれ互いに同一であっても異なっていてもよい。a'は２〜１６を表す。ｎは平均値であり０．５＜ｎ≦２０を表す。）
で表されるエポキシ樹脂、
（３）前記式（１’）においてａ'が３〜８であることを特徴とする前記（１）に記載のエポキシ樹脂、
（４）前記（１）〜（３）のいずれか一項に記載のエポキシ樹脂及び硬化剤を含有するエポキシ樹脂組成物、
（５）前記（４）に記載のエポキシ樹脂組成物を硬化してなる硬化物、
（６）下記式（２） That is, the present invention provides (1) the following formula (1)

(In the formula, plural Rs independently represent a hydrogen atom or a phenyl group.

Represents a substituted or unsubstituted cycloalkyl group having a carbon number, and may be the same or different from each other. a represents 3 to 17 (including alkylidene-bonded carbon). n is an average value and represents 0.5 <n ≦ 20. )
Epoxy resin represented by
(2) The following formula (1 ′)

(In the formula, plural Rs independently represent a hydrogen atom or a phenyl group.

May be the same as or different from each other. a 'represents 2-16. n is an average value and represents 0.5 <n ≦ 20. )
Epoxy resin represented by
(3) In the formula (1 ′), a ′ is 3 to 8, the epoxy resin according to (1),
(4) An epoxy resin composition containing the epoxy resin according to any one of (1) to (3) and a curing agent,
(5) Hardened | cured material formed by hardening | curing the epoxy resin composition as described in said (4),
(6) The following formula (2)

（式中、Ｒは水素原子もしくはフェニル基を表す。基

は、炭素数ａ個の置換または非置換のシクロアルキル基を表し、ａは３〜１７（アルキリデン結合の炭素を含む）を表す。）
で表されるフェノール系化合物をエピハロヒドリンとアルカリ金属水酸化物の存在下で反応させて、低分子量のエポキシ樹脂を得、該エポキシ樹脂とさらに前記式（２）のフェノール系化合物を反応させ、次いで貧溶媒を添加し結晶を析出させることを特徴とする前記（１）に記載のエポキシ樹脂の製造方法、
（７）下記式（２’）

（式中、Ｒは水素原子もしくはフェニル基を表す。ａは２〜１６を表す。）
で表されるフェノール系化合物をエピハロヒドリンとアルカリ金属水酸化物の存在下で反応させて、低分子量のエポキシ樹脂を得、該エポキシ樹脂とさらに前記式（２’）のフェノール系化合物を反応させ、次いで貧溶媒を添加し結晶を析出させることを特徴とする前記（２）または（３）に記載のエポキシ樹脂の製造方法
を、提供するものである。

(In the formula, R represents a hydrogen atom or a phenyl group.

Represents a substituted or unsubstituted cycloalkyl group having a carbon number, and a represents 3 to 17 (including carbon of an alkylidene bond). )
Is reacted with an epihalohydrin in the presence of an alkali metal hydroxide to obtain a low molecular weight epoxy resin, and the epoxy resin is further reacted with the phenolic compound of formula (2), The method for producing an epoxy resin according to (1), wherein a crystal is precipitated by adding a poor solvent,
(7) The following formula (2 ′)

(In the formula, R represents a hydrogen atom or a phenyl group. A represents 2 to 16.)
Is reacted in the presence of an epihalohydrin and an alkali metal hydroxide to obtain a low molecular weight epoxy resin, and the epoxy resin is further reacted with the phenolic compound of the formula (2 ′), Next, the method for producing an epoxy resin according to the above (2) or (3) is provided, wherein a crystal is precipitated by adding a poor solvent.

  The epoxy resin of the present invention is an epoxy resin having a very high molecular orientation, and has a property excellent in toughness and moisture resistance in the cured product, and is a composite material, an electric / electronic material, particularly a printed wiring board, It is useful for solder resists, semiconductor encapsulants, retardation films, molding materials, adhesives and the like.

  The epoxy resin raw material of the present invention is represented by the formula (2)

（式中、Ｒは水素原子もしくはフェニル基を表す。ａは３〜１７を表す。）で表されるフェノール系化合物が挙げられる。式（２）の化合物は環状ケトンとフェノールやフェニルフェノールとの重縮合反応により得ることが出来る。

(Wherein, R represents a hydrogen atom or a phenyl group, a represents 3 to 17). The compound of formula (2) can be obtained by a polycondensation reaction between a cyclic ketone and phenol or phenylphenol.

としては、シクロプロピリデン基、シクロブチリデン基、シクロヘキシリデン基、シクロペンチリデン基、アダマンチル基、フルオレニル基、３、３−ジメチル−５−メチルシクロヘキシリデン基、などが挙げられるが、結晶性の面から下記式 In the compound of formula (2), a group

Examples thereof include cyclopropylidene group, cyclobutylidene group, cyclohexylidene group, cyclopentylidene group, adamantyl group, fluorenyl group, 3,3-dimethyl-5-methylcyclohexylidene group, etc. The following formula from the aspect of sex

で表される基が好ましく、ａ’が３〜８であるシクロアルキリデン基が特に好ましい。

The cycloalkylidene group whose a 'is 3-8 is especially preferable.

  The compound of Formula (2) can also obtain a commercial item, for example, bisphenol Z, bisphenol CP, bisphenol TMC, bisphenol fluorene etc. are mentioned by a common name. These may be used alone or in combination of two or more.

  The production method of the epoxy resin of the present invention is roughly classified into a one-step method and a fusion method (also referred to as an advanced method or a two-step method. See, New Epoxy Resins Hiroshi Kakiuchi, pages 24-25 and 30-31). In the present invention, either the one-stage method or the fusion method may be used, but it is preferable to select the fusion method from the viewpoint of the simplicity of the production method. Hereinafter, the fusion method will be described in detail.

  In the fusion method, the phenolic compound represented by the formula (2) is reacted in the presence of epihalohydrin and an alkali metal hydroxide to obtain a low molecular weight epoxy resin, and further represented by the formula (2). The compound is reacted. After completion of this reaction, the epoxy resin of the present invention can be cooled as it is from the molten state and taken out as a resinous epoxy resin, but can be taken out as a crystalline compound if necessary. Specifically, it can be crystallized by a poor solvent or a temperature difference in the solution.

  In the fusion method, epichlorohydrin or epibromohydrin can be used as the epihalohydrin. The amount of epihalohydrin is usually 2 to 15 mol, preferably 3 to 12 mol, per 1 mol of the hydroxyl group of the compound of formula (2).

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like, and may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added to the reaction system and simultaneously under reduced pressure, or A method may be employed in which normal-pressure sewage and epihalohydrin are distilled and separated, water is removed, and epihalohydrin is continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-1.2 mol normally with respect to 1 equivalent of hydroxyl groups of the compound of Formula (2), Preferably it is 0.95-1.15 mol. The reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.

  Addition of alcohols such as methanol, ethanol, propanol and butanol, or aprotic polar solvents such as dimethyl sulfoxide and dimethyl sulfone is preferable for promoting the reaction.

  When using alcohol, the amount of its use is 3-30 weight% normally with respect to the quantity of epichlorohydrin, Preferably it is 5-20 weight%. When an aprotic polar solvent is used, the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.

  In addition, the reaction between the epihalohydrin and the compound of the formula (2) was added to the mixture of both as a quaternary ammonium salt catalyst such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and the like at 0.5 to 30 ° C. Hydrogen halide solid or aqueous solution of halohydrin ether compound of the formula (2) obtained by reacting for ˜8 hours is added and reacted at 20-100 ° C. for 1-10 hours for dehydrohalogenation (ring closure) ).

  Subsequently, excess epihalohydrin, a solvent, etc. are removed under the heat-reduced pressure after washing these epoxidation reaction products with water or without washing with water. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure. Can also be ensured. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of a compound of Formula (2), Preferably it is 0.05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is removed by heating under reduced pressure to give a low molecular weight epoxy resin (A) (represented by the above formula (1), n is an average value of 0.5) Or less). The epoxy equivalent of this epoxy resin (A) is usually 170 to 270 g / eq, and contains 70% (area% in gel permeation chromatography) of diglycidyl ether as a main component.

  Next, the epoxy resin (A) is further reacted with the compound represented by the formula (2). The charging ratio of the epoxy resin (A) to the phenolic compound of the formula (2) is generally 0.05 to 0. 0 with respect to 1 mol of the epoxy group of the epoxy resin (A). The ratio is 95 mol, preferably 0.1 to 0.9 mol.

  Although this chain extension reaction can be carried out without a catalyst, it is preferable to use a catalyst for promoting the reaction. Catalysts that can be used include triphenylphosphine, tetramethylammonium chloride, sodium hydroxide, potassium hydroxide, benzyltriphenylphosphonium chloride, butyltriphenylphosphonium, ethyltriphenylphosphonium iodide, ethyltriphenylphosphine. Examples include phonium bromide. The amount of the catalyst used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 1 mol of the epoxy group of the epoxy resin (A).

  In the chain extension reaction, a solvent is used as necessary. In particular, it is preferable to use a solvent in the sense of controlling the reaction temperature. Solvents that can be used include ketones such as cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, and acetone, esters such as ethyl acetate, butyl acetate, butyl lactate, and γ-butyrolactone, and aromatic hydrocarbons such as toluene and xylene. Etc. The amount of the solvent used is usually 5 to 150% by weight, preferably 10 to 100% by weight, based on the total weight of the epoxy resin (A) and the compound of the formula (2).

  The reaction temperature is usually 60 to 180 ° C, preferably 70 to 160 ° C. The progress of the reaction can be followed by GPC (gel permeation chromatography) or the like, and is performed until the compound of formula (2) is not completely detected. The completion of the reaction can also be traced by following the change in epoxy equivalent. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.

After completion of the reaction, the catalyst is removed from the obtained reaction mixture as necessary, and then the epoxy resin (B) of the present invention can be isolated by the following formulation. The reaction mixture can be used as it is as a varnish depending on the application.
(A) After melting at a temperature equal to or higher than the melting point or softening point of the epoxy resin of the present invention, it is taken out as a resin. (If a solvent is used, the solvent is distilled off under reduced pressure and then melted and resinated)
(B) Take out as a crystalline resin by crystallization.

The above (b) will be specifically described below.
In the formula (b), the epoxy resin of the present invention is precipitated by adding a poor solvent to the reaction mixture and cooling. Examples of the poor solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, methanol, ethanol, water and the like. The amount of the poor solvent to be added is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the epoxy resin (A) and the compound of the formula (2). After the crystals are precipitated, the epoxy resin (B) of the present invention can be obtained as a crystal powder by filtering and drying.

  In addition, when the condensation reaction is carried out without a solvent, after completion of the reaction, a good solvent for epoxy resin (B) such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, cyclopentanone, cyclohexanone, methyl ethyl ketone, etc. Dissolving the epoxy resin (B) of the present invention, and then adding a water-soluble poor solvent such as methanol, ethanol, isopropanol, and acetone, and further adding water to obtain a crystalline epoxy resin of the present invention with high yield. I can do it. In this case, the amount of the good solvent used is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the total weight of the epoxy resin (A) and the compound of formula (2). The amount of the water-soluble poor solvent used is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the theoretical yield of the epoxy resin. The amount of water used is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the epoxy resin (A) and the compound of formula (2).

The crystalline epoxy resin (B) thus obtained usually has a melting point of 70 to 180 ° C. A normal epoxy resin loses crystallinity due to the molecular weight distribution and becomes amorphous, but the epoxy resin of the present invention has a crystallinity when the molecular weight distribution is wide, and the orientation of the molecules is very strong. This orientation contributes to the improvement of physical properties.
The epoxy equivalent of the obtained epoxy resin is usually 200 to 2000 g / eq, preferably 250 to 1500 g / eq, more preferably 300 to 1000 g / eq.

  The obtained epoxy resin (B) may be used in the form of varnish, resinous solid, or crystalline resin in the preparation of the epoxy resin composition.

  Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin of the present invention can be used as a curable resin composition by combining with a curing agent, a curing accelerator, a cyanate resin and the like. Specific examples of applications include printed wiring boards, solder resists, semiconductor encapsulants, retardation films, molding materials, and adhesives.

  The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent as essential components. In the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  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.), phenols (phenol, alkyl-substituted phenol, aromatic substitution). 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, croton Polycondensates with aldehydes, cinnamaldehyde, etc., phenols and various diene compounds (disic) Polymers of pentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Acetophenone, benzophenone, etc.), phenols and aromatic dimethanol (benzenedimethanol, α, α, α ', α'-benzenedimethanol, biphenyldimethanol, α, α, α', polycondensates with α'-biphenyldimethanol, etc., polycondensates with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes. Condensation Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc., which are glycidylated products, alcohols, etc. It is not something. These 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, acid anhydride compounds, amide compounds, phenol compounds, and the like. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Meritic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, and modified products thereof, Examples include, but are not limited to, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent with respect to 1 equivalent of epoxy groups, or when exceeding 1.2 equivalent, in any case, curing may be incomplete, and good cured properties may not be obtained.

  A curing accelerator can also be used in the epoxy resin composition of the present invention. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4, 0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

  The epoxy resin composition of the present invention may contain an inorganic filler as necessary. Specific examples of the inorganic filler that can be used include silica, alumina, talc and the like. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention. Furthermore, various compounding agents such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and a pigment can be added to the epoxy resin composition of the present invention.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin composition of the present invention is mixed thoroughly with an epoxy resin, a curing agent and, if necessary, a curing accelerator, an inorganic filler and a compounding agent as necessary, using an extruder, kneader, roll, etc. until uniform. A cured product can be obtained by melting the epoxy resin composition after melting, molding it using a casting or transfer molding machine, and heating at 80 to 200 ° C. for 2 to 10 hours.

  An organic solvent can be added to the epoxy resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Aromatic solvents such as solvent, toluene, xylene and the like can be mentioned. The solvent is used in such a range that the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight.

  The epoxy resin composition of the present invention has a predetermined thickness after drying the above varnish on a planar support by various coating methods such as a gravure coating method, screen printing, metal mask method, and spin coating method known per se. It is also possible to obtain a sheet-like material by drying after coating so as to have a thickness of 5 to 100 μm, for example. In this case, which coating method is used is appropriately selected depending on the type, shape, size, and film thickness of the coating film. Examples of the base material include various polymers such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ether ketone, polyether imide, polyether ketone, polyketone, polyethylene, and polypropylene, and / or their co-polymers. A film made of a coalescence or a metal foil such as copper foil, particularly preferably polyimide or metal foil. Further, a sheet-like cured product can be obtained by further heating.

  In addition, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and is applied to a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnation and drying by heating can be subjected to hot press molding to obtain a cured product. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified.

Example 1
While performing a nitrogen purge on a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer, bisphenol Z (the following formula) as a phenol compound represented by the above formula (2)

商品名ＢｉｓＰ−Ｚ 本州化学株式会社製）１３４部に対しエピクロルヒドリン３７０部、メタノール２６部を仕込み撹拌下で約７０℃に昇温し、完全に溶解させた後、還流条件化でフレーク状水酸化ナトリウム４１部を１００分かけて分割添加した。その後、更に７０℃で１時間、後反応を行った。次いで水を１５０部加えて水洗を２回行い、加熱減圧下で油層から過剰のエピクロルヒドリンなどを除去した。残留分にメチルイソブチルケトン３１２部を加えて溶解し、７０℃で３０％水酸化ナトリウム水溶液１０部を加えて１時間反応を行った。反応後、水洗を３回行い生成塩などを除去した。加熱減圧下でメチルイソブチルケトンを留去し、エポキシ樹脂（Ａ１）１８３部を得た。得られたエポキシ樹脂のエポキシ当量は１９６ｇ／ｅｑ、形状は半固形であった。次いでこのエポキシ樹脂（Ａ１）９８部及び前記式（２）で表される化合物３３．５部を加えて撹拌下で溶解させ、ベンジルトリフェニルホスフォニウムクロライド０．０８部を添加した。１６０℃で４時間反応させＧＰＣにおいて前記式（２）の化合物が消えた後、更に反応を続け合計７時間反応させた後で１００℃まで冷却しジメチルスルホキシド１３２部を加えて得られた樹脂を溶解させた。更に６０℃まで冷却し撹拌下でメタノール１３２部を加えた。次いで３０℃にまで冷却し水２６４部を加えて結晶を析出させた。この結晶を濾過後乾燥させ白色粉末状の本発明のエポキシ樹脂（Ｂ１）１２６部を得た。このエポキシ樹脂（Ｂ１）のエポキシ当量は４８５ｇ／ｅｑ（式（１）のｎ≒２．０（平均値）、エポキシ当量より算出。）であった。得られたエポキシ樹脂（Ｂ１）の融点をＤＳＣ（示差熱分析計）で測定したところ、１０６℃であった。またＤＳＣの測定結果ではそのピークトップが二つ現れ、１１６℃と１４３℃であった。

(Product name BisP-Z manufactured by Honshu Chemical Co., Ltd.) 134 parts epichlorohydrin 370 parts and methanol 26 parts were charged and heated to about 70 ° C. with stirring. 41 parts of sodium were added in portions over 100 minutes. Thereafter, the post reaction was further carried out at 70 ° C. for 1 hour. Subsequently, 150 parts of water was added and washed with water twice, and excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. 312 parts of methyl isobutyl ketone was added to the residue and dissolved, and 10 parts of 30% aqueous sodium hydroxide solution was added at 70 ° C. and reacted for 1 hour. After the reaction, the product was washed with water three times to remove generated salts and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 183 parts of epoxy resin (A1). The epoxy equivalent of the obtained epoxy resin was 196 g / eq, and the shape was semi-solid. Next, 98 parts of this epoxy resin (A1) and 33.5 parts of the compound represented by the formula ( 2 ) were added and dissolved under stirring, and 0.08 part of benzyltriphenylphosphonium chloride was added. After the reaction at 160 ° C. for 4 hours and the compound of the above formula ( 2 ) disappeared in GPC, the reaction was further continued and reacted for a total of 7 hours, and then cooled to 100 ° C. Dissolved. Furthermore, it cooled to 60 degreeC and 132 parts of methanol was added with stirring. Next, the mixture was cooled to 30 ° C. and 264 parts of water was added to precipitate crystals. The crystals were filtered and dried to obtain 126 parts of a white powdery epoxy resin (B1) of the present invention. The epoxy equivalent of this epoxy resin (B1) was 485 g / eq (n≈2.0 (average value) of the formula (1), calculated from the epoxy equivalent). It was 106 degreeC when melting | fusing point of the obtained epoxy resin (B1) was measured by DSC (differential thermal analyzer). In the DSC measurement results, two peak tops appeared, 116 ° C. and 143 ° C.

Example 2 and Comparative Example 1
The epoxy resin (B1) of the present invention obtained in Example 1 as Example 2 and the high molecular weight bisphenol F type epoxy resin (YDF-2001, epoxy equivalent 471 g / eq. Manufactured by Toto Kasei Co., Ltd.) as Comparative Example 1 were used. Phenol novolak (Maywa Kasei Kogyo Co., Ltd., H-1, hydroxyl group equivalent 105 g / eq.) Was used as a curing agent, and triphenylphosphine (TPP) was added as a curing accelerator in the mixing ratio (parts by weight) shown in Table 1 below. Then, a composition was prepared, and a resin molded body was obtained by transfer molding, and cured at 140 ° C. for 6 hours and 170 ° C. for 2 hours.

Table 1
Example 2 Comparative Example 1
Epoxy resin B2 48.6
YDF-2001 47.1
Curing agent H-1 10.5 10.5
Curing accelerator TPP 0.7 0.7

Table 2 shows the results of measuring the physical properties of the cured product thus obtained. The physical property values were measured by the following methods.
Fracture toughness (K1C): ASTM E-399
Water absorption rate: 100 ° C./100%/weight increase rate after 48 hours

Table 2
Example 2 Comparative Example 1
Fracture toughness (K1C) (MPa) 49 32
Water absorption rate (%) 1.9 2.6

  As described above, the cured product of the epoxy resin composition of the present invention is excellent in toughness and moisture resistance.

Claims (4)

Following formula (1 ')

(In the formula, plural Rs independently represent a hydrogen atom or a phenyl group.

May be the same as or different from each other. a ′ represents 3 to 8 . n is an average value and represents 0.5 <n ≦ 20. )
The epoxy equivalent is 300 to 1000 g / eq. Epoxy resin composition containing an der Ru epoxy resin and a curing agent. The epoxy equivalent of the epoxy resin of Claim 1 is 485-1000 g / eq. The epoxy resin composition according to claim 1. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claim 1 or Claim 2 . The following formula (2 ')

(In the formula, R represents a hydrogen atom or a phenyl group. A ′ represents 3 to 8. )
Is reacted in the presence of an epihalohydrin and an alkali metal hydroxide to obtain a low molecular weight epoxy resin, and the epoxy resin is further reacted with the phenolic compound of the formula (2 ′), then the following formula you characterized by precipitating the added crystals antisolvent (1 ')
Following formula (1 ')

(In the formula, plural Rs independently represent a hydrogen atom or a phenyl group.

May be the same as or different from each other. a 'represents 3-8. n is an average value and represents 0.5 <n ≦ 20. )
In the manufacturing method of the e epoxy resin represented.