JP5142180B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin composition useful as a semiconductor sealing material, and a substrate material (a laminated board such as a printed wiring board or a build-up board, or a thermosetting or photosensitive solder resist), or an adhesive (such as bonding of substrates). About.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

  However, in recent years, with the development in the electric and electronic fields, the resin composition is highly purified, moisture resistance, adhesion, dielectric properties, low viscosity for high filler filling, and short molding cycle. There is a need for further improvements in various properties such as increased reactivity. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), the thinning is becoming more and more sophisticated year by year, and the properties required for the materials are not only heat resistance but also properties such as flexibility. It has become to. Furthermore, in recent years, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants for electrical and electronic parts as flame retardants due to environmental problems. It has been pointed out that it contributes to the generation of toxic substances such as As one method for solving the above problem, an epoxy resin having a phosphorus atom in the skeleton has been proposed. In particular, since a normal phosphate ester type compound has low stability, a cyclic phosphate compound having good stability is used. Even if a phosphoric acid ester compound is not used, those having excellent flame retardancy compared to conventional epoxy resins have been developed by selecting a resin skeleton. At present, flame retardancy called “halogen-free and phosphorus-free” is particularly demanded, and a resin skeleton that exhibits flame retardancy without using a flame retardant has been searched.

  In such a background, phenol-biphenylene type phenol resin and its reaction product with epihalohydrin are attracting attention as promising candidates. These require addition of an inorganic filler, but give a cured product having excellent flame retardance even under halogen-free and phosphorus-free conditions. Commercially available products include MEH-7851 series (phenol-biphenylene type phenol resin) manufactured by Meiwa Kasei Kogyo Co., Ltd., KAYAHARD GPH series (phenol-biphenylene type phenol resin) manufactured by Nippon Kayaku Co., Ltd., NC- 3000 series, CER-3000-L, and the like.

JP 2003-113225 A JP 2001-200031 A

  In recent years, however, adhesion to metals and toughness have been emphasized, and these improvements are urgently needed.

（式中、ｎは繰り返し数を示す。）
で表されるフェノール−ビフェニレン型フェノールアラルキル樹脂であって、ゲルパーミエーションクロマトグラフィーの測定においてｎ＝１とｎ＝２の間に現れるピークＰの面積比がｎ＝１のピーク面積に対し、０．０１５倍以上０．２倍未満であることを特徴とするフェノール樹脂およびエポキシ樹脂を含有するエポキシ樹脂組成物、
（２）
フェノール樹脂の繰り返し数ｎの平均値が１．０１〜３．５（ゲルパーミエーションクロマトグラフィーより算出）である上記（１）記載のエポキシ樹脂組成物、
（３）
ｎの平均値が１．１〜３．０である上記（２）記載のエポキシ樹脂組成物、
（４）
式（１）

（式中、ｎは繰り返し数を示す。）
フェノール−ビフェニレン型フェノールアラルキル樹脂において以下条件１に示すゲルパーミエーションクロマトグラフィーの測定においてｎ＝１とｎ＝２の間に現れるピークＰの面積比がｎ＝１のピーク面積に対し、０．０１５倍以上０．２倍未満であるフェノール樹脂とエピハロヒドリンとを反応させることにより得られるエポキシ樹脂、
（５）
上記（４）に記載のエポキシ樹脂を含有してなるエポキシ樹脂組成物、
（６）
エポキシ樹脂が、上記（４）に記載のエポキシ樹脂である上記（１）〜（３）のいずれか１項に記載のエポキシ樹脂組成物、
（７）
上記（１）〜（３）、（５）、（６）のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物、
に関する。 The present inventors have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention
(1)
Formula (1)

(In the formula, n represents the number of repetitions.)
The area ratio of the peak P that appears between n = 1 and n = 2 in the measurement of gel permeation chromatography is 0 with respect to the peak area of n = 1. An epoxy resin composition containing a phenol resin and an epoxy resin, wherein the epoxy resin composition is .015 times or more and less than 0.2 times;
(2)
The epoxy resin composition according to the above (1), wherein the average value of the phenol resin repeating number n is 1.01 to 3.5 (calculated from gel permeation chromatography),
(3)
The epoxy resin composition according to the above (2), wherein the average value of n is 1.1 to 3.0,
(4)
Formula (1)

(In the formula, n represents the number of repetitions.)
In the phenol-biphenylene type phenol aralkyl resin, the area ratio of the peak P appearing between n = 1 and n = 2 in the measurement of gel permeation chromatography shown in the following condition 1 is 0.015 with respect to the peak area of n = 1. An epoxy resin obtained by reacting a phenol resin and an epihalohydrin that are at least twice and less than 0.2 times,
(5)
An epoxy resin composition comprising the epoxy resin according to (4) above,
(6)
The epoxy resin composition according to any one of (1) to (3), wherein the epoxy resin is an epoxy resin according to (4) above,
(7)
Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of said (1)-(3), (5), (6),
About.

  The epoxy resin composition of the present invention has characteristics that are excellent in toughness and adhesion to metal in the cured product, semiconductor sealing material, and substrate materials (printed wiring boards, laminated boards such as build-up boards, Alternatively, it is useful for thermosetting or photosensitive solder resist) and adhesives (such as bonding of substrates).

  The epoxy resin composition (A) of the present invention comprises an epoxy resin and a formula (1)

（式中、ｎは繰り返し数を示す。）
で表されるフェノール−ビフェニレン型フェノールアラルキル樹脂を含有する。該フェノール−ビフェニレン型フェノールアラルキル樹脂は、そのゲルパーミエーションクロマトグラフィー（ＧＰＣ）の測定結果において、以下の図１に示すような２官能体（ｎ＝１）と３官能体（ｎ＝２）の間にピーク（以下、ピークＰという）が見られる。

(In the formula, n represents the number of repetitions.)
The phenol-biphenylene type phenol aralkyl resin represented by these is contained. The phenol-biphenylene type phenol aralkyl resin has a bifunctional (n = 1) and trifunctional (n = 2) as shown in FIG. 1 in the gel permeation chromatography (GPC) measurement results. A peak (hereinafter referred to as peak P) is observed between them.

In the present invention, physical properties are improved by paying attention to this peak P.
Specifically, the phenol resin is characterized in that the area ratio of the peak P is 0.015 times or more and less than 0.2 times the peak area of n = 1, more preferably 0.02 times or more and 0. Less than 17 times.
The peak P cannot be detected unless it is GPC with good resolution. As a specific example, it is preferable to use a column under the following conditions.
Model: Shodex SYSTEM-21
Column: KF-802, KF-802.5 (x 2) + KF-803 (4 in total)
Linked eluent: THF (tetrahydrofuran); 1 ml / min. 40 ° C
Detection: RI
Sample: About 0.4% THF solution (20 μl injection)

Hereinafter, the peak P will be described in detail.
The compound corresponding to the peak P does not have the structure of the formula (1) and is presumed to be a mixture of compounds containing a biphenyl group. The peak P is a preferable method for producing the phenol-biphenylene type phenol aralkyl resin in the present invention. In the reaction of a compound mainly composed of a compound represented by the following formula (2) with phenol, the peak P is expressed by the formula (2). and reaction products of secondary components and phenol contained, phenol - biphenylene type phenol aralkyl resin upon exposure to high temperature modified products, such as those partially bonded to (or during air oxidation) has expired and the like Conceivable.

（式中、Ｌは脱離基を示し、ハロゲン原子、Ｃ１〜Ｃ４のアルコキシメチル基、フェノキシ基、水酸基のいずれかを示す。）

(In the formula, L represents a leaving group and represents any one of a halogen atom, a C1-C4 alkoxymethyl group, a phenoxy group, and a hydroxyl group.)

  In general, it is known that physical properties are improved by using a high-purity compound, but in the present invention, physical properties such as adhesion and toughness are maintained while maintaining heat resistance and the like by reducing purity. Improvement was observed.

  There is no particular limitation on the number of repetitions n in the formula (1) of the phenol-biphenylene type phenol aralkyl resin (hereinafter referred to as phenol resin (a)) used in the present invention, but the n average value is 1.01 to 3.5. Preferably, it is 1.1-3.0 (measured value by GPC). When the average value of n exceeds 3.5, the effect of the peak P is not so remarkable and is difficult to understand.

  For example, the phenol resin (a) may be prepared by reacting the bismethylene biphenyl compound described in the formula (2) with phenol in accordance with, for example, the methods described in Patent Document 1 and Patent Document 2.

An example of the manufacturing method of a phenol resin (a) is shown below.
Examples of the compound represented by the formula (2) include biphenyl derivatives such as bismethoxymethylbiphenyl, bisethoxyethylbiphenyl, bishydroxymethylbiphenyl, bischloromethylbiphenyl, bisbromomethylbiphenyl, and bisphenoxymethylbiphenyl. As a general method for producing the compound of formula (2), biphenyl is reacted with formaldehyde (or a derivative thereof) and an acid (hydrochloric acid, hydrogen bromide, etc.) in the presence of a metal halide, and further purified from this. Halogenomethylbiphenyl is obtained. Further, by substituting this halogen atom with alcohol or water, a bishydroxy compound or a bisalkoxy compound can be obtained. These are appropriately purified by techniques such as distillation and recrystallization. In the present invention, it is preferable to select and use a biphenyl compound having a purity of 80 to 97% in the degree of purification at this time.

  Although the usage-amount of the phenol with respect to the biphenyl compound of Formula (2) is 1.5-30 mol normally with respect to 1 mol of compounds of Formula (2), 1.5-20 mol is especially preferable.

  In this reaction, an acid catalyst is used if necessary. Various acid catalysts can be used, but organic or inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid, p-toluenesulfonic acid, oxalic acid, Friedel such as stannic chloride, zinc chloride, ferric chloride, etc. Examples include crafts type catalysts. Since the orientation varies depending on the type of acid, it should be selected as necessary. The relationship is not clear, but those with higher acidity are often more para-oriented to phenol. The amount of the acid catalyst used varies depending on the type of the catalyst, but an appropriate amount may be added within the range of 0.0005 to 100% by weight with respect to the compound of the formula (2). (If it is only allowed to react, 0.0005 to 0.01 may be used, but a considerable amount of catalyst may be required for controlling the reaction.) In this reaction, the leaving group L is particularly halogenated. When it is an atom, hydrogen halide is generated as the reaction proceeds without adding a catalyst, and the reaction proceeds as this acts as a catalyst.

  In order to control the orientation in this reaction, a basic compound may be added. Specifically, a method based on the method described in JP-A-2003-301031 is preferable.

  The reaction temperature is usually 40 to 200 ° C, preferably 50 to 150 ° C. The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours. The reaction may be performed while charging all the raw materials at once, or may be performed by sequentially adding the compound of formula (2) in a state where phenol is kept at a constant temperature in advance. The reaction can be carried out without a solvent, but organic compounds such as toluene, monochlorobenzene, dichlorobenzene, lower alcohol and the like which are not directly involved in the reaction can also be used as a solvent.

  Of the compounds represented by formula (2), when L is a chlorine atom, the hydrochloric acid gas generated during the reaction is removed from the system by flowing an inert gas such as nitrogen gas, or removed under reduced pressure. It doesn't matter.

  After completion of the reaction, impurities such as hydrogen chloride and acid catalyst generated during the reaction are removed by neutralization and washing as necessary. Then, the target phenol resin (a) can be obtained by collect | recovering unreacted phenol and a solvent. The unreacted phenol compound and the solvent are preferably distilled off under heating and reduced pressure. It is also possible to blow off water vapor and distill it off with water vapor distillation.

  In the epoxy resin composition (A) of the present invention, the phenol resin (a) serves as a curing agent for the epoxy resin, and the phenol resin (a) can be used in combination with another epoxy resin curing agent. When used in combination, the proportion of the epoxy resin composition (A) of the present invention in the curing agent is preferably 5% by weight or more, particularly preferably 10% by weight or more.

  Examples of the curing agent that can be used in combination with the phenol resin (a) in the epoxy resin composition (A) of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Is mentioned. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Droxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polycondensates, phenols and polymers of various diene compounds (dicyclopentadiene, 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 excluding phenol and aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.), phenols excluding phenol and aromatic dichloromethyl Products (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), phenols excluding phenol and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) ), Polycondensates of bisphenols and various aldehydes, and modified products thereof, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, and the like, but are not limited thereto.

  In the epoxy resin composition (A) of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. . When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

  Specific examples of the epoxy resin that can be used in the epoxy resin composition (A) of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic Group-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde) , Crotonaldehyde, cinnamaldehyde, etc.), phenols and various diene compounds Polymers with dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl) Polycondensates with isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates with phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α, α Polycondensates with '-dichloroxylene, bischloromethylbiphenyl, etc.), phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenol) Glycidyl ether epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy, glycidylated alcohols, etc. Examples thereof include, but are not limited to, epoxy resins that are usually used. Moreover, although mentioned later, it is preferable to use the epoxy resin obtained by making the phenol resin which can be used for the epoxy resin composition of this invention react with epihalohydrin. These may be used alone or in combination of two or more.

  In addition to the phenol resin (a) and the epoxy resin, which are essential components, a curing accelerator may be used in combination. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Triethanolamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetraphenylphosphonium / tetraphenylborate, tetrasubstituted phosphonium / tetrasubstituted borate such as tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmol Such as tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like. When the curing accelerator is used, the amount used is 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, release agents, pigments, and various thermosetting resins may be added to the epoxy resin composition (A) of the present invention as necessary. it can. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The amount of these inorganic fillers varies depending on the use. For example, when used for a semiconductor encapsulant, the heat resistance, moisture resistance, mechanical properties, flame retardancy of the cured product of the epoxy resin composition (A) It is preferable to use it in the ratio which occupies 20 weight% or more in an epoxy resin composition (A) from surfaces, such as property, More preferably, it is 30 weight% or more, and it is used in the ratio which occupies 40 to 95 weight%. More preferred.

  Furthermore, the epoxy resin composition (A) of the present invention can contain known additives as required. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluorine resin, maleimide compound, cyanate resin (or its prepolymer), silicone Gel, silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, glass fiber, glass nonwoven fabric or carbon fiber Inorganic fillers such as, surface treatment agents for fillers such as silane coupling agents, release agents, colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

  The epoxy resin composition (A) of the present invention can be obtained by uniformly mixing the above components. And the epoxy resin composition (A) of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, an epoxy resin and a curing agent and, if necessary, a curing accelerator and an inorganic filler, a compounding agent, and various thermosetting resins are mixed thoroughly using an extruder, kneader, roll, etc. as necessary until uniform. Thus, the curable resin composition of the present invention is obtained, and the curable resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further at 80 to 200 ° C. A cured product can be obtained by heating for 10 hours.

  In addition, the epoxy resin composition (A) of the present invention may optionally contain a solvent. An epoxy resin composition (epoxy resin varnish) containing a solvent is formed by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. By this, it can be set as the hardened | cured material of the epoxy resin composition of this invention. The solvent content of the epoxy resin composition is usually about 10 to 70% by weight, preferably about 15 to 70% by weight, based on the total amount of the epoxy resin composition (A) of the present invention and the solvent. Moreover, the epoxy resin composition (A) containing this solvent can also be used as the following varnish. Examples of the solvent include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, tetra Sulfones such as methylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower alkylene glycol mono or di-lower alkyl ether, methyl ethyl ketone, Ketone-based solvents such as methyl isobutyl ketone, preferably di-lower alkyl ketones in which two alkyl groups may be the same or different; Emissions, and aromatic solvents such as xylene. These may be used alone or in combination of two or more.

  Moreover, a sheet-like adhesive can be obtained by applying the varnish on a release film, removing the solvent under heating, and performing B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  The cured product obtained in the present invention can be used for various applications. Specifically, general applications in which a thermosetting resin such as an epoxy resin is used can be mentioned. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRPs, etc.), insulating materials (printed boards, In addition to sealing agents, etc., additives to other resins and the like can be mentioned.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

Moreover, the epoxy resin (b) of this invention can be obtained by making a phenol resin (a) and epihalidin react.
The reaction for obtaining the epoxy resin (b) of the present invention is described below.

  The epoxy resin (b) of the present invention is obtained by reacting with an epihalohydrin using the phenol resin (a) as a raw material. As the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin and the like can be used. In the present invention, epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 3.0-20 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin (a) to be used, Preferably it is 3.0-10 mol.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.8-2.0 mol normally with respect to 1 mol of hydroxyl groups of a phenol resin (a), Preferably it is 0.9-1.5 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of the phenol resin (a) used.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure.

  Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin (b) is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the total hydroxyl group of bisphenols and biphenols used for epoxidation. It is. 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 distilled off under heating and reduced pressure to obtain the epoxy resin (b) of the present invention.

  The epoxy resin (b) of the present invention is a resinous or crystalline epoxy resin that is solid at room temperature, and its softening point or melting point is usually 40 to 200 ° C., and those prepared under preferred conditions are 40 to 180. It becomes ℃. When it is 40 ° C. or lower, it is semi-solid and difficult to handle. When it exceeds 200 ° C., problems such as difficulty in kneading occur when forming a composition. Moreover, the epoxy equivalent is 200-400 g / eq normally, and what was prepared on preferable conditions will be 230-330 g / eq.

  The epoxy resin (b) of the present invention can be derived into epoxy acrylate and its derivatives, carbonate resins, oxazolidone resins and the like. It can also be used as an additive for the photosensitive resin composition.

  The epoxy resin (b) of the present invention can be made into an epoxy resin composition (B) by combining with a curing agent. Hereinafter, the epoxy resin composition (B) using the epoxy resin (b) of the present invention will be described. In the epoxy resin composition (B) of the present invention, the epoxy resin (b) 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 (b) of the present invention in the epoxy resin is preferably 5% by weight or more, particularly preferably 10% by weight or more.

  Specific examples of other epoxy resins that can be used in combination with the epoxy resin (b) of the present invention are the same as the epoxy resins described in the above-mentioned epoxy resin composition (A).

  Examples of the curing agent 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, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Droxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polycondensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) , Phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α, α ' -Polycondensates with dichloroxylene, bischloromethylbiphenyl, etc.) Polycondensates with phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), bisphenols And polycondensates of aldehydes, and modified products thereof, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, and the like, but are not limited thereto. Moreover, it is preferable to use a phenol resin (a) as a hardening | curing agent.

  In the epoxy resin composition (B) of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin. . When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In addition, the epoxy resin composition (B) of the present invention may include various compounding agents such as a curing accelerator inorganic filler, a silane coupling material, a release agent, and a pigment, various thermosetting resins and additives as necessary. Etc. can be added. The thing which can be used is the same as the thing as described in the above-mentioned epoxy resin composition (A). The production method, curing method, and use of the composition (B) are the same as described in the epoxy resin composition (A).

  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. The present invention is not limited to these examples. Moreover, in the Example, the epoxy equivalent was measured by the method according to JIS K-7236, and the softening point according to JIS K-7234. The detection of peak P was measured by gel permeation chromatography. (Conditions as described above)

Synthesis example 1
Phenolic resin (a1)
While purging a flask equipped with a thermometer, condenser, fractionator, and stirrer with nitrogen purge, 242 parts of 4,4′-bismethoxymethylbiphenyl (purity 94%) and 188 parts of phenol were charged, and diethyl sulfate 7. Two parts were added dropwise. The reaction was carried out for 3 hours while maintaining the reaction temperature at 160 ° C. By-product methanol was reacted while distilling out of the system. After completion of the reaction, the reaction mixture was cooled, 300 parts of toluene was added and washed with water. From the organic layer, toluene and excess phenol were retained under heating and reduced pressure to obtain a phenol resin (a1). The physical property values are shown in Table 1 below.

Synthesis example 2
Phenolic resin (a2)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the purity of 4,4′-bismethoxymethylbiphenyl was 92% and the amount of phenol used was 209 parts. The physical property values are shown in Table 1 below.

Synthesis example 3
Phenolic resin (a3)
A flask equipped with a thermometer, a condenser tube, a fractionator tube, and a stirrer was purged with nitrogen, charged with 188 parts of phenol and maintained at 80 ° C., and then 4,4′-bischloromethylbiphenyl (purity 92%) 251 parts were added in portions over 4 hours. Further, the reaction was carried out at 80 ° C. for 4 hours. By-product hydrochloric acid was reacted while removing nitrogen out of the system. After completion of the reaction, the reaction mixture was cooled, 300 parts of toluene was added and washed with water. From the organic layer, toluene and excess phenol were retained under heating and reduced pressure to obtain a phenol resin (a3). The physical property values are shown in Table 1 below.

Synthesis example 4
Phenolic resin (a4)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the purity of 4,4′-bismethoxymethylbiphenyl was 92% and the amount of phenol used was 311 parts. The physical property values are shown in Table 1 below.

Synthesis example 5
Phenolic resin (a5)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the purity of 4,4′-bismethoxymethylbiphenyl was 92% and the amount of phenol used was 402 parts. The physical property values are shown in Table 1 below.

Synthesis Example 6
Phenolic resin (a6)
Synthesis was performed in the same manner as in Synthesis Example 2 except that the purity of 4,4′-bischloromethylbiphenyl was 94% and the amount of phenol used was 1413 parts. The physical property values are shown in Table 1 below.

Synthesis example 7
Phenolic resin (a7)
The synthesis was performed in the same manner as in Synthesis Example 5 except that the purity of 4,4′-bismethoxymethylbiphenyl was 98%. The physical property values are shown in Table 1 below.

Synthesis Example 8
Phenolic resin (a8)
The synthesis was conducted in the same manner as in Synthesis Example 4 except that the purity of 4,4′-bismethoxymethylbiphenyl was 98%. The physical property values are shown in Table 1 below.

＊ａ９；明和化成株式会社製 ＭＥＨ−７８５１ＳＳ

* A9; MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.

Examples 1 and 2 and Comparative Examples 1 and 2
Using the phenol resin shown in the following Table 2, it mix | blended with the compounding ratio (part by weight) shown in the following Table 2. A resin molding was obtained by transfer molding (175 ° C. 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

＊ＮＣ−３０００；日本化薬株式会社製 エポキシ樹脂 エポキシ当量２７７ｇ／ｅｑ．軟化点 ５７℃
＊ＴＰＰ；硬化促進剤 トリフェニルホスフィン 北興化学株式会社製

* NC-3000: Nippon Kayaku Co., Ltd. epoxy resin Epoxy equivalent 277 g / eq. Softening point 57 ℃
* TPP: Curing accelerator Triphenylphosphine made by Hokuko Chemical Co., Ltd.

Table 3 shows the results of measuring the physical properties of the obtained cured product. The physical property values were measured by the following methods.
TMA thermomechanical measuring device: TM-7000, manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
IZOD impact resistance test: JIS K-6911
Peel strength: JIS K-6911
Metal adhesion: SUS304 of 2.5 × 5.0 cm, 1.25 cm of aluminum plate, sandwiched with the above-mentioned epoxy resin composition, and pulled about a material cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. A shear test was performed. Average of 5 times.

  From the above results, it can be seen that the epoxy resin of the present invention retains heat resistance and is improved in fracture toughness and adhesion (peel strength, metal adhesion).

Reference example 3
223 parts of phenolic resin (a1) was charged with 555 parts of epichlorohydrin and 100 parts of methanol, heated to 65-70 ° C. with stirring, and then divided into 41 parts of flaky sodium hydroxide over 90 minutes under reflux conditions. Added. 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. The residue was dissolved by adding 600 parts of methyl isobutyl ketone, and 10 parts of a 30% aqueous sodium hydroxide solution was added at 70 ° C. for 1 hour. After the reaction, washing with water was performed 3 times to remove the generated salt and the like. It was obtained Dee epoxy resin distilling off the methyl isobutyl ketone (b1) by heating under reduced pressure. Table 4 shows the physical properties of the resin.

Reference example 4
To 218 parts of the phenol resin (a2), 555 parts of epichlorohydrin and 140 parts of dimethyl sulfoxide were charged, and the temperature was raised to 40 ° C. with stirring. Then, 41 parts of flaky sodium hydroxide was added in portions over 90 minutes. Thereafter, post-reaction was further performed at 40 ° C. for 2 hours and at 70 ° C. for 1 hour. Excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. The residue was dissolved by adding 600 parts of methyl isobutyl ketone, washed with water, and the generated salt was removed. The obtained organic layer was kept at 70 ° C., and further 10 parts of 30% aqueous sodium hydroxide solution was added to react for 1 hour. After the reaction, washing with water was performed 3 times to remove the generated salt and the like. It was obtained Dee epoxy resin distilling off the methyl isobutyl ketone (b2) by heating under reduced pressure. Table 4 shows the physical properties of the resin.

Example 5
Synthesis was performed in the same manner as in Example 3 except that 223 parts of the phenol resin (a1) was changed to 221 parts of the phenol resin (a3) to obtain the epoxy resin (b3) of the present invention. Table 4 shows the physical properties of the resin.

Example 6
The epoxy resin (b4) of the present invention was obtained by synthesizing in the same manner as in Example 3 except that 223 parts of the phenol resin (a1) was changed to 207 parts of the phenol resin (a4). Table 4 shows the physical properties of the resin.

Reference Example 7
Except that the phenol resin (a1) 223 parts were changed to a phenol resin (a6) 207 parts performing the same synthesis as in Example 4 to obtain d epoxy resin (b6). Table 4 shows the physical properties of the resin.

Comparative Example 3
Synthesis was performed in the same manner as in Example 4 except that 223 parts of the phenol resin (a1) was changed to 202 parts of the phenol resin (a7) to obtain a comparative epoxy resin (b7). Table 4 shows the physical properties of the resin.

Example 8, Comparative Example 4
For the epoxy resin (b4) of the present invention obtained in Example 6 and a comparative epoxy resin (b8) as a comparative example, a phenol novolak (phenol novolak, hydroxyl equivalent 106 g / eq. Hereinafter HD1) manufactured by Meiwa Kasei Kogyo Co., Ltd. As a curing accelerator, triphenylphosphine (TPP) was blended at a blending ratio (parts by weight) shown in Table 5 below. A resin molding was obtained by transfer molding (175 ° C. 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 6 shows the results of measuring the physical properties of the obtained cured product. The physical property values were measured by the following methods.
IZOD impact resistance test: JIS K-6911
Peel strength: JIS K-6911

  From the above results, it can be seen that the epoxy resin of the present invention has excellent properties in toughness and adhesion.

Claims (7)

Obtained by reacting a phenol with a biphenyl compound having a purity of 80 to 92%,
Formula (1)

(In the formula, n represents the number of repetitions, and an average value is 1.01 to 3.5.)
The peak P appearing between n = 1 and n = 2 in the measurement of gel permeation chromatography is 2.5 area% or more, and the area ratio is n = 0.15 times or more and less than 0.2 times the peak area of 1, an epoxy resin composition containing a phenol resin and an epoxy resin, wherein 1 equivalent of epoxy groups of the epoxy resin An epoxy resin composition containing 0.5 to 1.5 equivalents of the phenol resin. The peak P appearing between n = 1 and n = 2 in the measurement of gel permeation chromatography for the phenol-biphenylene type phenol aralkyl resin is 2.5 area% to 3.5 area%. Epoxy resin composition. The epoxy resin composition according to claim 2, wherein an average value of n is 1.1 to 3.0. Formula (1) obtained by reacting a phenol with a biphenyl compound having a purity of 80 to 92%

(In the formula, n represents the number of repetitions, and an average value is 1.01 to 3.5.)
In the measurement of gel permeation chromatography, the peak P appearing between n = 1 and n = 2 is 2.5 area% or more, and the area ratio is n = 1. An epoxy resin obtained by reacting a phenol resin and an epihalohydrin that are 0.015 times or more and less than 0.2 times the peak area. An epoxy resin composition comprising the epoxy resin according to claim 4 and a curing agent, wherein the epoxy resin contains 0.5 to 1.5 equivalents of a curing agent with respect to 1 equivalent of an epoxy group of the epoxy resin. Resin composition. The epoxy resin composition according to claim 1, wherein the epoxy resin is an epoxy resin according to claim 4. Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-3, 5, 6.