JP2006096992A - Epoxy resin composition, cured product thereof, new epoxy resin, new polyhydroxy compound, and methods for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition giving a cured product of high flame retardancy that is obtained even by using no halogen-based flame retardant, high in heat resistance, and suitably usable for semiconductor sealing materials or the like, to provide the cured product, to provide an epoxy resin suitably usable for the composition, to provide a polyhydroxy compound suitable as an intermediate and/or curing agent for the epoxy resin, and to provide methods for producing them respectively. <P>SOLUTION: The epoxy resin composition comprises (A) an epoxy resin and (B) a curing agent, wherein the epoxy resin has such a structure that two or more aromatic rings each having as substituent(s) on the aromatic ring (substituted) glycidyloxy group(s) and having alkyl groups on the 2, 4 and 6-sites of the glycidyloxy group are linked via two methylene groups bound to the respective aromatic rings of the biphenyl at the mutual meta-sites of the glycidyloxy group(s). The cured product of this composition, the new epoxy resin to be used for the composition, the intermediate for the new epoxy resin, and the new polyhydroxy compound as a curing agent for the epoxy resin, are also provided respectively. Further, the methods for producing them are also provided respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is excellent in curability and excellent in flame retardancy, heat resistance, etc. of the resulting cured product, and can be used in the electrical and electronic fields, particularly in semiconductor sealing materials, and the cured product thereof. The present invention relates to a novel epoxy resin which can be suitably used, an intermediate and / or a novel polyvalent hydroxy compound suitable as a curing agent, and a method for producing them.

  Epoxy resins can be cured with various curing agents, resulting in cured products that are generally excellent in low shrinkage (dimensional stability), electrical insulation, and chemical resistance during curing. In order to deal with technological innovations in the field of high-performance paints and environmental problems such as the dioxin problem, characteristics such as flame retardancy, heat resistance, moisture resistance, and curability that are superior to conventional ones are strongly demanded.

As means for meeting these demands, many phenol aralkyl resins and epoxy resins obtained by epoxidizing them have been proposed for the purpose of improving moisture resistance (Patent Example JP-A-63-238122). Kaihei 6-25392, JP-A-8-143648, etc.). However, even epoxy resin cured products using these compounds do not have sufficient performance to be applicable to current strict requirements. In these patent specifications, trialkylphenols are vaguely cited as examples of phenols to be used. However, there is no description of specific contents such as effects by using trialkylphenols.
On the other hand, as novolak-type resins, epoxy resins and epoxy resin compositions that give cured products with excellent water resistance, phenol aralkyl resins using trimethylphenols as raw materials and epoxy resins obtained by epoxidizing them have been proposed ( Patent Document 1). However, although this product is excellent in water resistance, sufficient flame retardancy cannot be obtained and heat resistance is also inferior, and the above technical problem cannot be solved. As phenols to be used, there are specific descriptions of 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, but 2,4,6-trialkylphenol. There is no example of the kind, and the present invention is not specifically disclosed.

  Regarding the reaction position of phenols when phenols react with aldehydes and xylylene-based condensing agents having a biphenyl skeleton represented by general formula (3), general formula (4) and general formula (5) described later. It is well known that ortho and para positions have overwhelming priority over meta positions. Therefore, the idea of using 2,4,6-trialkylphenols having only two meta positions as vacancies as a raw material for the reaction cannot usually be possessed by those skilled in the art. This is also a technical background in which trialkylphenols are not specifically described as raw materials for the above-mentioned phenol aralkyl resin.

JP-A-10-251362

  In the production method, when trimethylphenol other than 2,4,6-trimethylphenol is used, it is condensed with a biphenyl skeleton represented by general formula (3), general formula (4) and general formula (5). The resulting compound has very strong crystallinity and low solvent solubility. Therefore, in order to completely remove the catalyst used, a complicated operation such as filtration is required after the condensation reaction, and the yield decreases. Therefore, it was industrially disadvantageous. If the problem is only solvent solubility, even if trimethylphenol other than 2,4,6-trimethylphenol is used, the molar amount of trimethylphenol with respect to general formula (3) or (4) or (5) is reduced By reducing the n = 0 form, the crystallinity is lowered and the solubility is improved, but the viscosity of the epoxy resin obtained by reacting the obtained polyvalent hydroxy compound and epihalohydrin is greatly increased, which is not preferable.

  Therefore, the object of the present invention is excellent in curability and flame retardancy of a cured product obtained without using a halogen-based flame retardant, and has high heat resistance, and is suitable for use in semiconductor sealing materials and the like. Epoxy resin composition that can be used in the present invention, cured products thereof, novel epoxy resins that can be suitably used in the composition, novel polyhydric hydroxy compounds suitable as intermediates and / or curing agents, and production that can efficiently obtain them It is to provide a method.

  In order to solve the above-mentioned problems, the present inventors have intensively studied for an epoxy resin composition excellent in the above-mentioned properties. As a result, the glycidyloxy group which may have a substituent is substituted with a substituent on the aromatic ring. And two or more aromatic rings having an alkyl group having 1 to 4 carbon atoms which may be the same or different at the 2, 4, 6 positions of the glycidyloxy group are meta positions of the glycidyloxy group, An epoxy resin having a structure linked via two methylene groups which may have a substituent, and / or an aromatic hydroxyl group bonded to each aromatic ring of biphenyl, and the hydroxyl group 2 or more of the aromatic rings having an alkyl group having 1 to 4 carbon atoms which may be the same or different at the 2, 4 and 6 positions are bonded to each aromatic ring of biphenyl at the meta positions of the aromatic hydroxyl group. Have two substituents The cured product obtained by using a polyvalent hydroxy compound containing a structure linked via a methylene group may be methylated in comparison with the cured product obtained by using the epoxy resin proposed in Patent Document 1. Despite structural differences that differ only in the substitution position of the group, it has excellent flame resistance and heat resistance far beyond the expectations of those skilled in the art, and even without the use of halogen flame retardants. The inventors found that the flame retardancy of the UL-94 V-0 class was exhibited, and completed the present invention.

  That is, the present invention has an optionally substituted glycidyloxy group (a1) as a substituent on the aromatic ring, and may be the same or different at the 2, 4, 6 position of the glycidyloxy group. Two or more of the aromatic rings having an alkyl group (a2) having 1 to 4 carbon atoms have two substituents bonded to each aromatic ring of biphenyl at the meta positions of the glycidyloxy group (a1). An epoxy resin composition comprising an epoxy resin (A) including a structure linked via an optional methylene group (a3) and a curing agent (B) is provided.

  The present invention also provides an aromatic ring having an aromatic hydroxyl group (c1) and an alkyl group having 1 to 4 carbon atoms (c2) which may be the same or different at positions 2, 4, and 6 of the hydroxyl group. Are linked to each other via the methylene group (a3) which may have a substituent at the meta position of the aromatic hydroxyl group (c1) and bonded to each aromatic ring of biphenyl. An epoxy resin composition comprising a polyvalent hydroxy compound (C) having a structure and an epoxy resin (D) is also provided.

  Further, the present invention provides the following general formula (1)

（式中、Ｒ^１は同一でも異なっていてもよい炭素数１〜４のアルキル基、Ｒ^２は同一でも異なっていてもよい水素原子またはメチル基、Ｒ^３は同一でも異なっていてもよい水素原子または炭素数１〜４のアルキル基、ｎは平均値で０〜１０を示す。）で表されるエポキシ樹脂をも提供する。

Wherein R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and R ³ is the same or different hydrogen. An epoxy resin represented by an atom or an alkyl group having 1 to 4 carbon atoms, and n is an average value of 0 to 10) is also provided.

  Further, the present invention provides the following general formula (2)

（但し、Ｒ^１は同一でも異なっていてもよい炭素数１〜４のアルキル基、Ｒ^２は同一でも異なっていてもよい水素原子またはメチル基、ｎは平均値で０〜１０を示す。）で表される多価ヒドロキシ化合物をも提供する。

(However, R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and n is an average value of 0 to 10.) The polyvalent hydroxy compound represented by these is also provided.

Further, the present invention is represented by trialkylphenols (x1) having an alkyl group having 1 to 4 carbon atoms as substituents at positions 2, 4, 6 and the following general formulas (3), (4) and (5). A method for producing a polyvalent hydroxy compound, comprising reacting at least one biphenyl compound (x2) selected from the group consisting of the following compounds, and reacting these polyvalent hydroxy compounds with epihalohydrin: An epoxy resin manufacturing method is also provided. (X in the formula represents a halogen atom, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  According to the present invention, it is possible to obtain an epoxy resin composition having good flame retardancy of a cured product obtained without using a halogen-based flame retardant, and excellent in heat resistance. It is possible to provide a novel epoxy resin suitable for a product, a novel polyvalent hydroxy compound suitable as a curing agent and a raw material for the epoxy resin, a production method thereof, and a cured product using them. These are extremely useful as epoxy resin materials in the field of electronic materials such as semiconductor encapsulating materials and printed wiring boards that meet environmental and safety problems.

Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the epoxy resin composition according to the first aspect of the present invention has a glycidyloxy group (a1) which may have a substituent as a substituent on the aromatic ring, and the glycidyl Two or more aromatic rings having an alkyl group (a2) having 1 to 4 carbon atoms which may be the same or different at the 2,4,6 position of the oxy group are meta positions of the glycidyloxy group (a1), and biphenyl It has the structure connected via the methylene group which may have a substituent of two couple | bonded with each aromatic ring. From the viewpoint of excellent flame retardancy of the resulting cured product, it is preferable that all of the alkyl groups (a2) having 1 to 4 carbon atoms on the aromatic ring are methyl groups.

  Examples of the two methylene groups optionally having a substituent bonded to each aromatic ring of the biphenyl include those having the following structures. In addition, it shows having couple | bonded with the meta position of the said aromatic ring in the position of * mark in the following structural formula.

  Specific examples of these structures include the following structures.

  Among these, from the viewpoint of excellent curability of the epoxy resin composition, the glycidyloxy group (a1) preferably has a structure having no substituent, and the industrial production method of the epoxy resin is easy. The linking group is preferably a methylene group having no substituent (the above structural formula (x)).

  The epoxy resin (A) in the epoxy resin composition of the present invention contains the above structure as its repeating unit, but the epoxy resin may contain other structures. You may use together with the other epoxy resin which has the structure of. Moreover, it is although it does not specifically limit as an epoxy equivalent of an epoxy resin (A), It is 300-700 g / eq from the point which is excellent in performance balance, such as a flame retardance of a hardened | cured material obtained, heat resistance, and moisture resistance. Preferably there is.

  Here, as a method for obtaining the epoxy resin (A), for example, trialkylphenols (x2) having an alkyl group having 1 to 4 carbon atoms as substituents at the 2, 4, 6 positions and the general formula (3), ( Examples thereof include a method of reacting one or more biphenyl compounds (x2) selected from the group consisting of the compounds represented by 4) and (5) and reacting the resulting polyvalent hydroxy compound with epihalohydrin.

  Specific examples of the trialkylphenols (a) having a C 1-4 alkyl group as a substituent at the 2,4,6 positions include 2,4,6-trimethylphenol and 2,4,6-triethylphenol. 2,4-dimethyl-6-ethylphenol, 2,4,6-tripropylphenol and the like. Of these, 2,4,6-trimethylphenol is preferred because the balance between flame retardancy, heat resistance and curability is improved.

  Examples of the compound represented by the general formula (3), (4) or (5) include bis (chloromethyl) biphenyl, bis (bromomethyl) biphenyl, bis (dimethylol) biphenyl, bis (methoxymethyl) biphenyl, Bis (ethoxymethyl) biphenyl, bis (isopropoxy) methylbiphenyl, bis (hydroxyethyl) biphenyl, bis (1-methoxy-1-ethyl) biphenyl, bis (1-isopropoxy-1-ethyl) biphenyl, bis (2 -Hydroxy-2-propyl) biphenyl, bis (2-methoxy-2-propyl) biphenyl, bis (2-isopropoxy-2-propyl) biphenyl, bis (vinyl) biphenyl and the like. Among these, bis (chloromethyl) biphenyl or bis (methoxymethyl) biphenyl is preferable because the balance between flame retardancy, heat resistance and curability is improved. Moreover, only 1 type may be used for the compound represented by these general formula (3), (4) or (5), and it may use it in combination of 2 or more types. In addition, the xylylene-type condensing agent which has a biphenyl skeleton represented by General formula (3), General formula (4), and General formula (5) is represented.

  As a reaction for obtaining this polyvalent hydroxy compound, it is preferable to use an acid catalyst. The acid catalyst can be appropriately selected from various inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, paratoluenesulfonic acid, methanesulfonic acid, zinc chloride, aluminum chloride, iron chloride, boron trifluoride, etc. Or a solid acid such as activated clay, silica-alumina or zeolite. Among these, methanesulfonic acid and paratoluenesulfonic acid are preferable because a reaction product having a high number of nuclei is easily obtained. That is, it is most preferable to react 2,4,6-trimethylphenol and the biphenyl in the presence of methanesulfonic acid and / or paratoluenesulfonic acid. Although the usage-amount of these catalysts is not specifically limited, It is preferable to use 0.1-30 weight% of the compound represented by General formula (3)-(5). The form of these catalysts is not particularly limited, and the catalyst may be used in the form of an aqueous solution or in the form of a solid.

  Moreover, when making the said trialkylphenol (x1) and a carbonyl group containing compound (x2) react, with respect to 100 weight part of trialkylphenols (x1), phenol and a C1-C4 monoalkylphenol are further provided. And 5 to 30 parts by weight of at least one alkylphenol (x3) selected from dialkylphenols having 1 to 4 carbon atoms can be reacted with the carbonyl group-containing compound (x2). By using the alkylphenols (x3) in combination, the flame retardancy of the resulting cured product is improved, the compatibility of the reaction product is increased, and a polynuclear hydroxy compound having a high nucleus number can be easily obtained. it can.

  Moreover, when making the said trialkylphenol (x1) and biphenyl compound (x2) react, with respect to 100 weight part of trialkylphenols (x1), phenol, a C1-C4 monoalkylphenol, and carbon are further added. The carbonyl group-containing compound (x2) can be reacted with 5 to 30 parts by weight of at least one alkylphenol (x3) selected from dialkylphenols having 1 to 4 formulas. By using the alkylphenols (x3) in combination, the flame retardancy of the resulting cured product is improved, the compatibility of the reaction product is increased, and a polynuclear hydroxy compound having a high nucleus number can be easily obtained. it can.

  Since the alkylphenols (x3) are excellent in the effect of improving the flame retardancy of the resulting cured product, methylphenols such as o-cresol, m-cresol, p-cresol, 2,4-dimethylphenol, 2 Dimethylphenols such as 2,6-dimethylphenol, 2,5-dimethylphenol and 3,4-dimethylphenols are preferred, especially 2,4-dimethylphenol, 2,6-dimethylphenol and 2,5-dimethylphenol. It is preferable to use it.

  When performing the above reaction, the ratio of the total number of moles of trialkylphenols (x1) and alkylphenols (x3) to the number of moles of the carbonyl group-containing compound (x2) [(x1) + (x3)]: (x2) Is preferably 5: 0.1 to 1: 1 (molar ratio). At this time, it is preferable to distill off the excessively used trialkylphenols (x1) under reduced pressure heating in order to inhibit the heat resistance of the cured product.

  The condensation reaction can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight, based on the total weight of the charged raw materials. The reaction temperature is usually 40 to 180 ° C., and the reaction time is usually 1 to 10 hours. These organic solvents can be used alone or in combination of several kinds. In addition, it is preferable to distill off water or alcohols generated during the reaction out of the system using a fractionating tube or the like in order to carry out the reaction quickly.

  Moreover, when the coloring of the compound of General formula (1) obtained is large, in order to suppress it, you may add antioxidant and a reducing agent. Although it does not specifically limit as antioxidant, For example, a hindered phenol type compound, such as a 2, 6- dialkylphenol derivative, a bivalent sulfur type compound, a phosphite type compound containing a trivalent phosphorus atom, etc. are mentioned. Can do. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. What is necessary is just to perform a neutralization process and a water washing process in accordance with a conventional method. For example, when an acidic catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline are used, and when a basic catalyst is used, hydrochloric acid, sodium monohydrogen phosphate, An acidic substance such as succinic acid can be used as a neutralizing agent. Subsequently, after neutralizing or washing with water, the solvent and unreacted substances are distilled off under heating under reduced pressure to concentrate the product, whereby the polyhydric phenol compound can be obtained.

  Next, the polyhydric phenol compound and epihalohydrin can be reacted to obtain an epoxy resin. The conditions for carrying out the epoxy resin reaction can be carried out by various methods. For example, 2-10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group of the polyhydric phenol compound, and 0.9-2. The reaction is carried out at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 0 mol of a basic catalyst. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  When industrial production is performed, the first batch of epoxy resin production uses all of the prepared epihalohydrin, but after the next batch, the epihalohydrin recovered from the crude reaction product and the amount consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferable because it is easily available.

  The basic catalyst is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity for the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide, potassium hydroxide, and calcium hydroxide. In use, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After washing the reaction product of these epoxidation reactions, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight based on the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

The curing agent (B) used in the first invention is not particularly limited, and various curing agents can be used as long as they can undergo a curing reaction with the epoxy group in the epoxy resin (A). I can do it. For example, various curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds can be used. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. Examples of amide compounds include dicyandiamide and linolenic acid. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydroanhydride. Examples thereof include phthalic acid, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, and aromatic compounds. Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol Condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group) ), Polyphenol compounds such as aminotriazine-modified phenol resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.), and Examples of these modified products include, but are not limited to, these. These may be used alone or in combination of two or more.

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-polymer are used because the cured product obtained has excellent flame retardancy. A condensed novolak resin, a naphthol-cresol co-condensed novolak resin, a biphenyl-modified phenol resin, a biphenyl-modified naphthol resin, and an aminotriazine-modified phenol resin are preferable. Linkages containing aromatic rings that do not have hydroxyl groups, such as modified phenolic resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenolic resins Is preferably polyvalent aromatic compound containing an aromatic ring are linked structure having a hydroxyl group by. In addition, aromatic ring 2 having an aromatic hydroxyl group (c1), which will be described later, and having an alkyl group having 1 to 4 carbon atoms (c2) which may be the same or different at positions 2, 4, and 6 of the hydroxyl group. A structure in which two or more meta groups of the aromatic hydroxyl group (c1) are linked via two methylene groups (a3) which may have a substituent, bonded to each aromatic ring of biphenyl. The polyvalent hydroxy compound (C) containing is particularly preferably the following general formula (2)

（但し、Ｒ^１は同一でも異なっていてもよい炭素数１〜４のアルキル基、Ｒ^２は同一でも異なっていてもよい水素原子またはメチル基、ｎは平均値で０〜１０を示す。）で表される多価ヒドロキシ化合物を用いることも好ましい。

(However, R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and n is an average value of 0 to 10.) It is also preferable to use a polyvalent hydroxy compound represented by

  Although it does not restrict | limit especially as a compounding quantity of the said hardening | curing agent (B), From the point that the mechanical physical property etc. of the hardened | cured material obtained are favorable, with respect to 1 equivalent of epoxy groups in an epoxy resin composition. The amount of the active group in the curing agent is preferably 0.7 to 1.5 equivalents.

  The epoxy resin composition according to the second invention of the present invention has an aromatic hydroxyl group (c1) and may be the same or different at the 2, 4, 6 position of the hydroxyl group. Two or more methylene groups which may have a substituent, in which two or more of the aromatic rings having the group (c2) are at the meta positions of the aromatic hydroxyl group (c1) and bonded to each aromatic ring of biphenyl It contains a polyvalent hydroxy compound (C) having a structure linked via a3) and an epoxy resin (D).

  Specific examples of the structure of the polyvalent hydroxy compound (C) include the following. In addition, the line segment drawn from the aromatic ring in the following structural formula indicates a bond with another structure.

  The epoxy resin (D) is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetra Methylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol Novolac epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon Formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resins are not limited thereto. Moreover, these epoxy resins may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl is preferable in terms of excellent flame retardancy of the resulting cured product. Type epoxy resin is preferred. Furthermore, it is preferable to use the above-mentioned epoxy resin (A) from the viewpoint that the obtained cured product can have both flame retardancy and heat resistance at a high level.

  Further, the blending amount of the polyhydric phenol resin (C) is not particularly limited, but the epoxy group 1 in the epoxy resin composition is preferable because the obtained cured product has good mechanical properties. The amount by which the active group in the curing agent is 0.7 to 1.5 equivalents relative to the equivalent is preferred.

  In the first and second epoxy resin compositions of the present invention, in addition to the above, a curing accelerator may be used in combination as necessary. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5,4,0] -undecene (DBU) is preferred.

  The epoxy resin composition of the present invention has high flame retardancy of the resin itself, and a cured product having flame retardancy can be obtained without using a flame retardant, but it is particularly high in use in the electrical and electronic fields. In applications where flame retardancy at the level is required, it is preferable to further add a flame retardant. At this time, the non-halogen flame retardant (E), which can cope with the environment and safety, is used because it reaches a practical level without using a halogen flame retardant having a generally high flame retardant effect. Things are preferable.

  The non-halogen flame retardant (E) is blended in a resin composition or the like to impart flame retardancy, and can be used without any limitation as long as it does not substantially contain a halogen atom. Is possible.

  The fact that it does not substantially contain a halogen atom means that a halogen-based compound is not blended for the purpose of imparting flame retardancy, and a trace impurity halogen of about 5000 ppm or less derived from epihalohydrin contained in an epoxy resin is not contained. It may be included.

  The non-halogen flame retardant (E) is a compound that does not substantially contain a halogen atom such as chlorine or bromine and has a function as a flame retardant or a flame retardant aid. For example, phosphorus flame retardant (e1), nitrogen flame retardant (e2), silicone flame retardant (e3), inorganic flame retardant (e4), organometallic salt flame retardant (e5), etc. There are no restrictions on the use of these, and they may be used alone or in combination with a plurality of flame retardants of the same system, or a combination of flame retardants of different systems may be used. It is.

  As the phosphorus flame retardant (e1), both inorganic and organic compounds can be used as long as they are compounds containing phosphorus atoms. Examples of inorganic compounds include phosphoric acids such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, which may be subjected to surface treatment for the purpose of preventing hydrolysis and the like. Examples thereof include inorganic nitrogen-containing phosphorus compounds such as ammonium and phosphoric acid amide.

  Examples of the surface treatment method of red phosphorus include (1) coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. A method of treating, (2) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and a thermosetting resin such as a phenol resin, and (3) magnesium hydroxide. There is a method of doubly coating with a thermosetting resin such as a phenol resin on a coating of an inorganic compound such as aluminum hydroxide, zinc hydroxide or titanium hydroxide, and any of (1) to (3) What was processed by the method of can also be used.

  Examples of the organic phosphorus compounds include phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, and organic nitrogen-containing phosphorus compounds.

  Specific examples of the phosphoric ester compound include triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di-2,6-xylenol phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl). Phosphate), resorcinyl diphenyl phosphate, and the like.

  Specific examples of the phosphonic acid compound include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, and phosphonic acid metal salts described in JP-A No. 2000-226499.

  Specific examples of the phosphinic acid compound include diphenylphosphinic acid, methylethylphosphinic acid, a compound described in JP-A-2001-55484, 9,10-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = Cyclic organophosphorus compounds such as 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  Specific examples of the phosphine oxide compound include triphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, diphenylphosphinyl hydroquinone, JP-A No. 2000-186186, JP-A No. 2002-080484, JP-A No. 2002. -097248 gazette etc. are mentioned.

  Specific examples of the phosphorane compound include compounds described in JP-A No. 2000-281871.

  Examples of organic nitrogen-containing phosphorus compounds include JP 2002-60720, JP 2001-354686, JP 2001-261792, JP 2001-335703, JP 2000-103939, and the like. And the phosphazene compounds described.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant (e1), the other components of the epoxy resin composition, and the desired degree of flame retardancy. In 100 parts by weight of the epoxy resin composition containing all of the flame retardant and other fillers and additives, when using red phosphorus, it is preferably blended in the range of 0.1 to 2.0 parts by weight, Similarly, when an organophosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by weight, particularly preferably in the range of 0.5 to 6.0 parts by weight.

  Further, the method of using the phosphorus-based flame retardant (e1) is not particularly limited. For example, JP-A-2002-08056, JP-A-2002-053734, JP-A-2000-248156, The combined use of hydrotalcite described in Kaihei 9-235449, the combined use of magnesium hydroxide described in JP-A-2001-329147, etc., JP-A-2002-23989, JP-A-2001-323134, etc. A combination of the above described boron compounds, a combination of zirconium oxide described in JP-A No. 2002-069271, etc., a combination of black dyes described in JP-A No. 2001-123047, etc., and JP-A No. 2000-281873 Combined use of calcium carbonate, combined use of zeolite described in JP 2000-281873 A, etc. Combined use of zinc molybdate as described in JP 2000-248155 A, etc., combined use of activated carbon as described in JP 2000-212392 A, JP 2002-348440 A, JP 2002-265758 A, 2002 The surface treatment methods described in JP-A No. 180053, JP-A No. 2001-329147, JP-A No. 2001-226564, JP-A No. 11-269345 and the like can be applied.

  The nitrogen-based flame retardant (e2) is not particularly limited as long as it is a compound containing a nitrogen atom, and examples thereof include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, triazine compounds, A cyanuric acid compound and an isocyanuric acid compound are preferable.

  Specific examples of the triazine compound include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and derivatives thereof. For example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, melam sulfate, (2) phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamine, benzoguanamine, acetoguanamine, formguanamine, etc. A co-condensate of melamines and formaldehyde, (3) a mixture of the co-condensate of (2) and a phenol resin such as a phenol formaldehyde condensate, (4) said (2) and (3) are further paulownia oil, Opposite sex Such as those modified with linseed oil, and the like.

  Specific examples of the cyanuric acid compound include cyanuric acid, melamine cyanurate, diallyl monoglycidyl isocyanuric acid, monoallyl diglycidyl isocyanuric acid, and the like.

  Specific examples of the isocyanuric acid compound include tris (β-cyanoethyl) isocyanurate.

Further, the compound containing a nitrogen atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. May be.

  The amount of the nitrogen-based flame retardant (e2) is appropriately selected depending on the type of the nitrogen-based flame retardant (e2), other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, it is preferable to mix in the range of 0.05 to 10 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, flame retardant, and other fillers and additives. It is preferable to mix | blend in the range of 0.1-5 weight part.

  Further, the method of using the nitrogen-based flame retardant (e2) is not particularly limited. For example, a combination of metal hydroxides described in JP 2001-234036 A, JP 2002-003577 A, and the like. The combined use of molybdenum compounds described in JP-A-2001-098144 and the like can be applied.

  The silicone flame retardant (e3) is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  Specific examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, and the like.

  Specific examples of the silicone rubber include methyl silicone rubber and methylphenyl silicone rubber.

  Specific examples of the silicone resin include methyl silicone, methyl phenyl silicone, and phenyl silicone.

The organic compound containing a silicon atom has a functional group such as —OH, —NH ₂ , —NCO, —COOH, —CHO, —SH, methylol, acrylate, methacrylate, silyl, glycidyl group or epoxy group. You may do it.

  The amount of the silicone flame retardant (e3) is appropriately selected according to the type of the silicone flame retardant (e3), the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, it is preferable to mix in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, flame retardant and other fillers and additives.

  Further, the method of using the silicone-based flame retardant (e3) is not particularly limited. For example, a combination of molybdenum compounds described in JP-A-2001-011288, JP-A-10-182941, etc. Conventional methods such as the combined use of the described alumina can be applied.

  Examples of the inorganic flame retardant (e4) include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low-melting glass.

  Specific examples of the metal hydroxide include, for example, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, JP 2002-212391 A, and JP 2001. Examples thereof include composite metal hydroxides described in JP-A No. 335681 and JP-A No. 2001-32050.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The amount of the inorganic flame retardant (e4) is appropriately selected depending on the type of the inorganic flame retardant (e4), the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, it is preferable to mix in the range of 0.05 to 20 parts by weight in 100 parts by weight of the epoxy resin composition containing all of the epoxy resin, curing agent, flame retardant and other fillers and additives. It is preferable to mix in the range of 5 to 15 parts by weight.

  Further, the method of using the inorganic flame retardant (e4) is not particularly limited. For example, a method for controlling the specific surface area described in JP-A No. 2001-226564, JP-A No. 2000-19595, JP-A-2000-191886, JP-A-2000-109647, JP-A-2000-038776, etc., methods for controlling the shape, particle size and particle size distribution, JP-A-2001-32050, JP-A-2000 No. 095956, JP-A-10-279813, JP-A-10-251486, etc., surface treatment, nitric acid described in JP-A-2002-030200, JP-A-2001-279063, etc. Combined use of metal salts, combined use of zinc borate described in JP 2001-049084 A, JP 2000-1959 In combination with inorganic powders described in No. 4 etc., in combination with butadiene rubber described in JP 2000-156437 A, etc., high acid value polyethylene wax and long chain alkyl phosphates described in JP 2000-053875 A, etc. A combination of a series compound can be applied.

  Examples of the organometallic salt flame retardant (e5) include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. Examples thereof include an ionic bond or a coordinate bond compound.

  Specific examples of the acetylacetonate metal complex include compounds described in JP-A No. 2002-265760.

  Specific examples of the organometallic carbonyl compound include compounds described in JP-A No. 2002-371169.

  Specific examples of the organic cobalt salt compound include, for example, a cobalt naphthenic acid complex, a cobalt ethylenediamine complex, a cobalt acetoacetonate complex, a cobalt piperidine complex, a cobalt cyclohexanediamine complex, a cobalt tetraazacyclotetradodecane complex, and a cobalt ethylenediaminetetraacetic acid complex. , Cobalt tetraethylene glycol complex, cobalt aminoethanol complex, cobalt cyclohexadiamine complex, cobalt glycine complex, cobalt triglycine complex, cobalt naphthidirine complex, cobalt phenanthroline complex, cobalt pentanediamine complex, cobalt pyridine complex, cobalt salicylic acid complex, cobalt Salicylaldehyde complex, cobalt salicylideneamine complex, cobalt complex porphyrin, cobalt thiourea complex And the like can be given.

  Specific examples of the organic sulfonic acid metal salt include potassium diphenylsulfone-3-sulfonate.

  Specific examples of the compound in which the metal atom and the aromatic compound or heterocyclic compound are ion-bonded or coordinate-bonded include compounds described in JP-A-2002-226678.

  The amount of the organic metal salt flame retardant (e5) is appropriately selected depending on the type of the organic metal salt flame retardant (e5), the other components of the epoxy resin composition, and the desired degree of flame retardancy. However, for example, in 100 parts by weight of an epoxy resin composition containing all of an epoxy resin, a curing agent, a flame retardant, and other fillers and additives, it may be blended in the range of 0.005 to 10 parts by weight. preferable.

  Various compounding agents, such as a silane coupling agent, an ion trap agent, a mold release agent, and a pigment, can be added to the epoxy resin composition of the present invention as necessary.

  Applications of the epoxy resin composition of the present invention include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, insulation paints And coating materials such as resist ink, conductive paste, and the like. Among these, it can be suitably used as a semiconductor sealing material.

  When using the epoxy resin composition of the present invention as a semiconductor encapsulant material, an inorganic filler (F) is further blended with the above-described epoxy resin, curing agent and non-halogen flame retardant (E). Accordingly, there may be mentioned a method obtained by adding other components and thoroughly mixing until uniform using an extruder, kneader, roll or the like. The semiconductor encapsulating material thus obtained is a non-halogen flame retardant resin composition, which is environmentally friendly and safe.

  Examples of the inorganic filler (F) include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the blending amount of the filler (F) is particularly large, it is preferable to use fused silica. As the fused silica, either crushed or spherical shape can be used, but the blending amount is increased and the melt viscosity of the molding material is increased. In order to suppress the increase in the amount, it is particularly preferable to use mainly spherical ones. In order to further increase the blending amount of the spherical silica, it is preferable that the particle size distribution of the spherical silica is appropriately adjusted so that the average particle size is 5 to 30 μm. The filling rate is particularly preferably 65 to 95% by weight with respect to the total amount of the epoxy resin composition, from the viewpoint of good flame retardancy of the resulting cured product. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can also be used.

  The resin composition of the present invention is used to encapsulate electronic components such as semiconductor elements and manufacture a semiconductor device by molding by various methods such as casting, transfer molding, compression molding, injection molding, etc. In addition, it may be further heated at 80 to 200 ° C. for 2 to 10 hours as necessary.

  When the epoxy resin composition of the present invention is used as a resin composition for electronic circuit boards, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone. Can be manufactured. The amount of the solvent used at this time is usually 10 to 70% by weight, preferably 15 to 65% by weight, particularly preferably 35 to 65% by weight in the resin composition for electronic circuit boards. In addition, as a method of obtaining the molded cured product, the resin composition for an electronic circuit board is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and dried by heating. After obtaining and laminating, a method of hot press molding it can be mentioned. Specific examples of the electronic circuit board include a printed wiring board, a printed circuit board, a flexible printed wiring board, and a build-up wiring board.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of apply | coating to a resist ink hardened | cured material is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  When the epoxy resin composition of the present invention is used as a coating material such as an adhesive or paint, the composition may be melted and coated, or a solution obtained by dissolving the composition in the solvent is usually used. After coating by this method, the solvent may be removed by drying and cured. At this time, the curing catalyst may be used as necessary. Moreover, you may mix the said inorganic filler etc.

  The cured product of the present invention is obtained by molding and curing the above-described epoxy resin composition of the present invention, and can be used as a laminate, a cast product, an adhesive, a coating film, a film and the like. The curing method is not particularly limited. For example, after uniformly mixing an epoxy resin, a curing agent, other curing agents blended as necessary, various compounding agents, etc., room temperature or 80 to 200 ° C. The method of heat-curing can be mentioned. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the epoxy resin composition prepared according to the above-mentioned various uses.

  Epoxy resin of the present invention represented by the following general formula (1)

（式中、Ｒ^１は同一でも異なっていてもよい炭素数１〜４のアルキル基、Ｒ^２は同一でも異なっていてもよい水素原子またはメチル基、Ｒ^３は同一でも異なっていてもよい水素原子または炭素数１〜４のアルキル基、ｎは平均値で０〜１０を示す。）で表されるエポキシ樹脂である。

Wherein R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and R ³ is the same or different hydrogen. An atom or an alkyl group having 1 to 4 carbon atoms, and n represents an average value of 0 to 10).

Among these, it is preferable from the point which is excellent in the flame retardance of the cured | curing material that R < ¹ >, R < ³ > in the said General formula (1) is a methyl group.

  Among these, those having the structural formulas (x), (y), and (z) in the skeleton are preferable, and those having the structural formulas (6a1), (7a1), (8a1), and (9a1) are particularly preferable. Is preferred.

  The melt viscosity (ICI viscometer method, 150 ° C.) of the epoxy resin is preferably 5 dPa · s or less, and the epoxy equivalent is not particularly limited. In view of excellent performance balance such as heat resistance and moisture resistance, it is preferably 300 to 700 g / eq.

  The polyvalent hydroxy compound (C) of the present invention has the following general formula (2)

(However, R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and n is an average value of 0 to 10.) It is represented by

Among these, it is preferable from the point which is excellent in the flame retardance of the cured | curing material that R < ¹ >, R < ³ > in the said General formula (2) is a methyl group.

  Further, among these, those having the structural formulas (x), (y), (z) in the skeleton are preferable, and the structural formulas (6-1), (7-1), (8-1), Those having (9-1) are preferred.

  The hydroxyl equivalent of the polyvalent hydroxy compound is not particularly limited, but is 200 to 700 g / eq from the viewpoint of excellent performance balance such as flame retardancy, heat resistance and moisture resistance of the obtained cured product. Is preferred.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The melt viscosity and GPC measurement at 150 ° C. were measured under the following conditions.

Melt viscosity at 150 ° C .: Conforms to ASTM D4287 GPC:
Equipment Tosoh Corporation HLC-8220 GPC
Column: Tosoh Corporation TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL
Solvent: Tetrahydrofuran Flow rate: 1 ml / min
Detector: RI

Example 1 [Synthesis of polyvalent hydroxy compound (A-1)]
Example 1 To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, the following formula (10)

で表される化合物２４２部、２，４，６−トリメチルフェノール９５２部を仕込み、室温下、窒素を吹き込みながら撹拌した。メタンスルホン酸９部を発熱に注意しながら液温が８０℃を超えないようにゆっくり添加した。その後油浴中で１５０℃まで加熱し、分留管を用いて生成するメタノールを抜き出した後、更に５時間反応させた。反応終了後、更にメチルイソブチルケトン１４００部を加え、分液ロートに移し水洗した。次いで洗浄水が中性を示すまで水洗後、有機層から溶媒及び未反応の２，４，６−トリメチルフェノールを加熱減圧下に除去し、下記式（１１）

242 parts of a compound represented by the formula, and 952 parts of 2,4,6-trimethylphenol were charged and stirred at room temperature while blowing nitrogen. 9 parts of methanesulfonic acid was slowly added so as not to exceed 80 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 150 ° C. in an oil bath, and methanol produced was extracted using a fractionating tube, followed by further reaction for 5 hours. After completion of the reaction, 1400 parts of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. Then, after washing with water until the washing water shows neutrality, the solvent and unreacted 2,4,6-trimethylphenol are removed from the organic layer under heating and reduced pressure, and the following formula (11)

（式中、ｎの平均値は０．２である。）で表される本発明の多価ヒドロキシ化合物（Ａ−１）４３７部を得た。得られた多価ヒドロキシ化合物の融点は２１２℃（ＤＳＣ法）、水酸基当量は２４０ｇ／ｅｑであった。Ｃ_１３−ＮＭＲチャート（図１）からその構造を確認した。に示す。

(In the formula, the average value of n is 0.2.) 437 parts of the polyvalent hydroxy compound (A-1) of the present invention represented by the following formula was obtained. The obtained polyvalent hydroxy compound had a melting point of 212 ° C. (DSC method) and a hydroxyl group equivalent of 240 g / eq. The structure was confirmed from the C ₁₃ -NMR chart (FIG. 1). Shown in

Example 2 [Synthesis of Epoxy Resin (B-1)]
A flask equipped with a thermometer, a dropping funnel, a condenser tube, and a stirrer was purged with nitrogen gas, while 240 parts of the polyhydroxy compound (A-1) obtained in Example 1 and 463 g of epichlorohydrin (5.0 mol) were obtained. 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain the following formula (12)

（式中、ｎの平均値は０．３である。）で表される本発明のエポキシ樹脂（Ｂ−１）２８０部を得た。得られたエポキシ樹脂の軟化点は８０℃、１５０℃の溶融粘度は４．８ｄＰａ・ｓ、エポキシ当量は３２１ｇ／ｅｑであった。Ｃ_１３−ＮＭＲチャート（図２）からその構造を確認した。

In the formula, 280 parts of the epoxy resin (B-1) of the present invention represented by the following formula was obtained. The resulting epoxy resin had a softening point of 80 ° C., a melt viscosity at 150 ° C. of 4.8 dPa · s, and an epoxy equivalent of 321 g / eq. The structure was confirmed from the C ₁₃ -NMR chart (FIG. 2).

Example 3 Synthesis of polyvalent hydroxy compound (A-2)
In Example 1, instead of 2,4,6-trimethylphenol, 11 parts by weight of 2,4-dimethylphenol and 5 parts by weight of 2,6-trimethylphenol were added to 100 parts by weight of 2,4,6-trimethylphenol. 440 parts of the polyvalent hydroxy compound (A-1) of the present invention was obtained in the same manner as in Example 1 except that dimethylphenol was used. The obtained polyvalent hydroxy compound had a softening point of 80 ° C. (ball and ring method) and a hydroxyl group equivalent of 239 g / eq. The structure was confirmed from the C ₁₃ -NMR chart (FIG. 3). .

Example 4 [Synthesis of Epoxy Resin (B-2)]
In Example 2, 291 parts of the epoxy resin (B-1) of the present invention was used in the same manner as in Example 2 except that the polyvalent hydroxy compound (A-2) was used instead of the polyvalent hydroxy compound (A-1). Got. The resulting epoxy resin had a softening point of 72 ° C., a melt viscosity at 150 ° C. of 2.7 dPa · s, and an epoxy equivalent of 331 g / eq. The structure was confirmed from the C ₁₃ -NMR chart (FIG. 4).

Comparative Example 1 [Synthesis of Multivalent Hydroxy Compound (C)]
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, the following formula (10)

で表される化合物２４２部、２，３，６−トリメチルフェノール９５２部を仕込み、室温下、窒素を吹き込みながら撹拌した。メタンスルホン酸９部を発熱に注意しながら液温が８０℃を超えないようにゆっくり添加した。その後油浴中で１５０℃まで加熱し、分留管を用いて生成するメタノールを抜き出した後、更に５時間反応させた。反応終了後、更にメチルイソブチルケトン１４００部を加え、不溶解成分を濾過にて除去し、濾過液を分液ロートに移し洗浄水が中性となるまで水洗した。一方、濾過にて除去した不溶解成分も洗浄水が中性となるまで水洗し、これを水洗後の濾過液に加え分散させた。不溶解物を分散させた濾過液から溶媒及び未反応の２，３，６−トリメチルフェノールを加熱減圧下に除去し、下記式（１３）

242 parts of a compound represented by the formula and 952 parts of 2,3,6-trimethylphenol were added and stirred at room temperature while blowing nitrogen. 9 parts of methanesulfonic acid was slowly added so as not to exceed 80 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 150 ° C. in an oil bath, and methanol produced was extracted using a fractionating tube, followed by further reaction for 5 hours. After completion of the reaction, 1400 parts of methyl isobutyl ketone was further added, insoluble components were removed by filtration, the filtrate was transferred to a separatory funnel and washed with water until the washing water became neutral. On the other hand, insoluble components removed by filtration were also washed with water until the washing water became neutral, and this was added to the filtrate after washing and dispersed. The solvent and unreacted 2,3,6-trimethylphenol were removed from the filtrate with the insoluble material dispersed under heating and reduced pressure, and the following formula (13)

（式中、ｎの平均値は０．２である。）で表される多価ヒドロキシ化合物（Ｃ）４０２部を得た。得られた多価ヒドロキシ化合物の融点は２２５℃（ＤＳＣ法）、水酸基当量は２４３ｇ／ｅｑであった。

(In the formula, the average value of n is 0.2.) 402 parts of a polyvalent hydroxy compound (C) represented by the following formula was obtained. The obtained polyvalent hydroxy compound had a melting point of 225 ° C. (DSC method) and a hydroxyl group equivalent of 243 g / eq.

Comparative Example 2 [Synthesis of Epoxy Resin (D)]
In Example 2, in the same manner as in Example 2 except that 243 g of the polyvalent hydroxy compound (C) is used instead of the polyvalent hydroxy compound (A-1), the following formula (14)

（式中、ｎの平均値は０．３である。）で表されるエポキシ樹脂（Ｄ）２７３部を得た。得られたエポキシ樹脂の軟化点は８３℃（ボール＆リング法）、１５０℃の溶融粘度は５．２ｄＰａ・ｓ、エポキシ当量は３２７ｇ／ｅｑであった。

(In the formula, the average value of n is 0.3.) 273 parts of an epoxy resin (D) represented by the following formula was obtained. The resulting epoxy resin had a softening point of 83 ° C. (ball and ring method), a melt viscosity at 150 ° C. of 5.2 dPa · s, and an epoxy equivalent of 327 g / eq.

Comparative Example 3 [Synthesis of Multivalent Hydroxy Compound (E)]
In Comparative Example 1, in the same manner as in Comparative Example 1 except that 2,3,5-trimethylphenol is used instead of 2,3,6-trimethylphenol, the following formula (15)

（式中、ｎの平均値は０．２である。）で表される多価ヒドロキシ化合物（Ｅ）４０５部を得た。得られた多価ヒドロキシ化合物の融点は２１９℃（ＤＳＣ法）、水酸基当量は２４２ｇ／ｅｑであった。

(In the formula, the average value of n is 0.2.) 405 parts of a polyvalent hydroxy compound (E) represented by the following formula was obtained. The obtained polyvalent hydroxy compound had a melting point of 219 ° C. (DSC method) and a hydroxyl group equivalent of 242 g / eq.

Comparative Example 4 [Synthesis of Epoxy Resin (F)]
In Example 2, in the same manner as in Example 2 except that 242 g of the polyvalent hydroxy compound (E) is used instead of the polyvalent hydroxy compound (A-1), the following formula (16)

(In the formula, the average value of n is 0.3.) 275 parts of an epoxy resin (F) represented by the following formula was obtained. The resulting epoxy resin had a softening point of 80 ° C., a melt viscosity at 150 ° C. of 4.9 dPa · s, and an epoxy equivalent of 328 g / eq.

Comparative Example 5 [Synthesis of Multivalent Hydroxy Compound (G)]
In Comparative Example 1, in the same manner as in Comparative Example 1 except that 3,4,5-trimethylphenol is used instead of 2,3,6-trimethylphenol, the following formula (17)

(In the formula, the average value of n is 0.2.) 402 parts of a polyvalent hydroxy compound (G) represented by the following formula was obtained. The obtained polyvalent hydroxy compound had a melting point of 231 ° C. (DSC method) and a hydroxyl group equivalent of 245 g / eq.

Comparative Example 6 [Synthesis of Epoxy Resin (H)]
In Example 2, in the same manner as in Example 2 except that 245 g of the polyvalent hydroxy compound (G) is used instead of the polyvalent hydroxy compound (A-1), the following formula (18)

（式中、ｎの平均値は０．３である。）で表されるエポキシ樹脂（Ｈ）２７０部を得た。得られたエポキシ樹脂の軟化点は８５℃、１５０℃の溶融粘度は５．８ｄＰａ・ｓ、エポキシ当量は３３２ｇ／ｅｑであった。

In the formula, 270 parts of an epoxy resin (H) represented by the following formula was obtained. The resulting epoxy resin had a softening point of 85 ° C., a melt viscosity at 150 ° C. of 5.8 dPa · s, and an epoxy equivalent of 332 g / eq.

Examples 5-10 and Comparative Examples 7-15
Various materials shown in Tables 1 to 5 were used, and in accordance with the formulations shown in Tables 1 to 5, melt-kneading was performed for 10 minutes at a temperature of 100 ° C. using two rolls to obtain the desired composition. About the obtained epoxy resin composition, gel time was measured with the following method and sclerosis | hardenability was tested. In addition, this was press-molded at 180 ° C. for 10 minutes, and then further cured at 180 ° C. for 5 hours. Then, a test piece having a thickness of 1.6 mm in accordance with the UL-94 test method was prepared and cured by the following method. The physical properties of the material were confirmed.

  Gel time: 0.15 g of the epoxy resin composition is placed on a cure plate heated to 175 ° C. (manufactured by THERMO ELECTRIC), and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.

Glass transition temperature: Measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method; frequency 1 Hz, temperature rising rate 3 ° C./min).
Flame retardancy: Based on the UL-94 test method, a flame test was performed using five test pieces having a thickness of 1.6 mm.

In addition, * 1- * 3 in a table | surface means the following.
* 1: No formulation was obtained due to crystallization.
* 2: Not gelled.
* 3: The specimen was not cured and could not be obtained.

  Examples 1-4 which are the epoxy resin curing agent and epoxy resin of the present invention are compared with similar compounds made from trialkylphenol other than 2,4,6-trialkylphenol as in Comparative Examples 1-6, It can be produced in a high yield without requiring complicated operations such as unnecessary filtration. On the other hand, Examples 5-8 using the epoxy resin composition containing the epoxy resin of the present invention are similar compounds using trialkylphenol as a raw material other than 2,4,6-trialkylphenol as in Comparative Examples 7-12. Compared to, it is excellent in flame retardancy, heat resistance and curability. On the other hand, Examples 9 to 10 using the epoxy resin composition containing the epoxy resin curing agent of the present invention were prepared using trialkylphenol as a raw material other than 2,4,6-trialkylphenol as in Comparative Examples 13 to 15. Compared to similar compounds, there is no problem that a cured product cannot be produced, and the flame retardancy, heat resistance, and curability are excellent.

3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 2. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 3. FIG. 3 is a ¹³ C-NMR spectrum of the polyvalent hydroxy compound obtained in Example 4.

Claims (19)

The glycidyloxy group (a1) which may have a substituent has 1 to 4 carbon atoms which may be the same or different at the 2, 4 and 6 positions of the glycidyloxy group as a substituent on the aromatic ring. Two or more methylene groups which may have a substituent, in which two or more of the aromatic rings having an alkyl group (a2) are in the meta positions of the glycidyloxy group (a1) and bonded to each aromatic ring of biphenyl ( An epoxy resin composition comprising an epoxy resin (A) having a structure linked through a3) and a curing agent (B). The epoxy resin composition according to claim 1, wherein the alkyl group (a2) having 1 to 4 carbon atoms is a methyl group. Two or more aromatic rings having an aromatic hydroxyl group (c1) and having an alkyl group having 1 to 4 carbon atoms (c2) which may be the same or different at positions 2, 4, and 6 of the hydroxyl group are aromatic. A polyvalent hydroxy group having a structure in which two meta groups of the aliphatic hydroxyl group (c1) are linked to each aromatic ring of biphenyl and linked via a methylene group (a3) which may have a substituent. An epoxy resin composition comprising a compound (C) and an epoxy resin (D). The epoxy resin composition according to claim 3, wherein the alkyl group (c2) having 1 to 4 carbon atoms is a methyl group. The epoxy resin (D) has a glycidyloxy group (a1) which may have a substituent as a substituent on the aromatic ring, and is the same or different at the 2, 4 and 6 positions of the glycidyloxy group. Two or more of the aromatic rings having an alkyl group having 1 to 4 carbon atoms (a2) may be meta-positions of the glycidyloxy group (a1), and two substituents bonded to each aromatic ring of biphenyl. The epoxy resin composition according to claim 4, which is an epoxy resin (A) comprising a structure linked through a methylene group (a3) which may have. The following general formula (1)

Wherein R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and R ³ is the same or different hydrogen. An epoxy resin represented by an atom or an alkyl group having 1 to 4 carbon atoms, and n represents an average value of 0 to 10. The epoxy resin according to claim 6, wherein R ¹ in the general formula (1) is a methyl group. 7. The epoxy resin according to claim 6, having a melt viscosity (ICI viscometer method, 150 ° C.) of 5 dPa · s or less. The following general formula (2)

(However, R ¹ is the same or different alkyl group having 1 to 4 carbon atoms, R ² is the same or different hydrogen atom or methyl group, and n is an average value of 0 to 10.) The polyvalent hydroxy compound represented by these. The polyvalent hydroxy compound according to claim 9, wherein R ¹ is a methyl group. From the group consisting of trialkylphenols (x1) having an alkyl group having 1 to 4 carbon atoms as substituents at positions 2, 4, 6 and compounds represented by the following general formulas (3), (4) and (5) A method for producing a polyvalent hydroxy compound, comprising reacting one or more selected biphenyl compounds (x2).

(X in the formula represents a halogen atom, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) In addition to 100 parts by weight of trialkylphenols (x1) having an alkyl group having 1 to 4 carbon atoms as substituents at the 2,4,6 positions, phenol, monoalkylphenols having 1 to 4 carbon atoms and 1 to 1 carbon atoms The method for producing a polyvalent hydroxy compound according to claim 10, wherein 5 to 30 parts by weight of one or more alkylphenols (x3) selected from 4 dialkylphenols are reacted with the biphenyl compound (x2). The ratio [[(x1) + (x3)] / (x2)] of the total number of moles of trialkylphenols (x1) and alkylphenols (x3) to the number of moles of biphenyl compound (x2) is 5: 0.1 The method for producing a polyvalent hydroxy compound according to claim 10, 11 or 12, which is ˜1: 1 (molar ratio). The manufacturing method of the epoxy resin characterized by making the polyhydric hydroxy compound and epihalohydrin of Claim 9 or 10 react. The epoxy resin composition according to any one of claims 1 to 5, further comprising a non-halogen flame retardant (E). The non-halogen flame retardant (E) is a phosphorus flame retardant (e1), a nitrogen flame retardant (e2), a silicone flame retardant (e3), an inorganic flame retardant (e4), and an organic metal salt flame retardant ( The epoxy resin composition according to claim 15, which is one or more flame retardants selected from the group consisting of e5). The epoxy resin composition according to claim 15 or 16, which is a semiconductor sealing material. The epoxy resin composition according to claim 17, which is a non-halogen flame retardant resin composition. Hardened | cured material which hardened the epoxy resin composition of any one of Claims 1-5, 15-18.

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