JP3938592B2 - Phenolic compounds - Google Patents
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- JP3938592B2 JP3938592B2 JP2006215154A JP2006215154A JP3938592B2 JP 3938592 B2 JP3938592 B2 JP 3938592B2 JP 2006215154 A JP2006215154 A JP 2006215154A JP 2006215154 A JP2006215154 A JP 2006215154A JP 3938592 B2 JP3938592 B2 JP 3938592B2
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本発明は耐熱性、耐水性、機械的強度に優れる硬化物を与えるエポキシ樹脂の原料として有用なフェノール化合物に関する。 The present invention relates to a phenol compound useful as a raw material for an epoxy resin that gives a cured product having excellent heat resistance, water resistance and mechanical strength.
エポキシ樹脂は種々の硬化剤で硬化させることにより、一般的に機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などの優れた硬化物となり、接着剤、塗料、積層板、成形材料、注型材料などの幅広い分野に利用されている。従来、工業的に最も使用されているエポキシ樹脂としてビスフェノ−ルＡにエピクロルヒドリンを反応させて得られる液状および固形のビスフェノ−ルＡ型エポキシ樹脂がある。その他液状のビスフェノ−ルＡ型エポキシ樹脂にテトラブロムビスフェノ−ルＡを反応させて得られる難燃性固形エポキシ樹脂などが汎用エポキシ樹脂として工業的に使用されている。 Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, molding It is used in a wide range of fields such as materials and casting materials. Conventionally, epoxy resins most industrially used include liquid and solid bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin. In addition, a flame retardant solid epoxy resin obtained by reacting tetrabromobisphenol A with a liquid bisphenol A type epoxy resin is industrially used as a general-purpose epoxy resin.
しかしながら、前記したような汎用エポキシ樹脂は分子量が大きくなるにつれて、それを硬化して得られる硬化物の靭性は増加するものの耐熱性が低下するという欠点がある。また、耐熱性の低下を補うためにクレゾールノボラックエポキシ樹脂などの多官能エポキシ樹脂を混合した場合に得られる硬化物は耐熱性は高くなるものの、靭性は低下し吸水率が高くなるという欠点がある。一方、最近の電子産業などの目ざましい発達に伴い、これらに使用される電気絶縁材料などに要求される耐熱性、耐水性及び機械強度（例えば靭性）は益々厳しくなっており、これらの特性に優れたエポキシ樹脂の出現が待ち望まれている。またこれらの特性を満たすエポキシ樹脂として、特許文献１にビフェニル骨格を有するエポキシ樹脂が記載されているが、それが具体的に開示するエポキシ樹脂は、耐水性、機械強度は優れているものの、官能基数が２であるため、耐熱性の点で十分とはいえない。 However, the general-purpose epoxy resin as described above has a drawback that, as the molecular weight increases, the toughness of a cured product obtained by curing it increases, but the heat resistance decreases. In addition, a cured product obtained by mixing a polyfunctional epoxy resin such as a cresol novolac epoxy resin to compensate for a decrease in heat resistance has a drawback that although the heat resistance increases, the toughness decreases and the water absorption increases. . On the other hand, with recent remarkable developments in the electronics industry, the heat resistance, water resistance and mechanical strength (for example, toughness) required for the electrical insulating materials used in these are becoming increasingly severe and excellent in these characteristics. The emergence of new epoxy resins is awaited. In addition, as an epoxy resin satisfying these characteristics, an epoxy resin having a biphenyl skeleton is described in Patent Document 1, but the epoxy resin specifically disclosed therein is excellent in water resistance and mechanical strength, Since the number of bases is 2, it cannot be said that heat resistance is sufficient.
本発明者らはこうした実状に鑑み、耐熱性、耐水性及び機械的強度に優れる硬化物を与えるエポキシ樹脂を求めて鋭意研究した結果、本発明を完成させるに到った。 In light of these circumstances, the present inventors have intensively studied for an epoxy resin that gives a cured product having excellent heat resistance, water resistance, and mechanical strength, and as a result have completed the present invention.
すなわち本発明は、下記式（２） That is, the present invention provides the following formula (2)
（式中、ｎは平均値を示し１．１〜２．１の値を取る。Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、アリール基のいずれかを表し個々のＲは互いに同一であっても異なっていてもよい。Ｐは水素原子またはメチル基を表す。）
で表される化合物を提供するものである。
(In the formula, n represents an average value and takes a value of 1.1 to 2.1. R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and each R represents They may be the same or different from each other, and P represents a hydrogen atom or a methyl group.)
The compound represented by these is provided.
本発明の化合物は、耐熱性及び耐水性及び機械的強度に優れた特性を兼ね備えた硬化物を与えるエポキシ樹脂の原料となるフェノール化合物であり、成形材料、注型材料、積層材料、塗料、接着剤、レジストなど広範囲の用途にきわめて有用である。 The compound of the present invention is a phenolic compound that is a raw material of an epoxy resin that gives a cured product having excellent heat resistance, water resistance and mechanical strength, and is a molding material, a casting material, a laminated material, a paint, an adhesive It is extremely useful for a wide range of applications such as agents and resists.
本発明の化合物は、下記式（２） The compound of the present invention has the following formula (2)
（式中ｎ、Ｐ及びＲは式（２）におけるのと同じ意味を表す。）
で表され、本発明の化合物とエピハロヒドリンとの反応をアルカリ金属水酸化物の存在下で行うことにより得ることができる。
(In the formula, n, P and R have the same meaning as in formula (2).)
It can be obtained by carrying out the reaction between the compound of the present invention and epihalohydrin in the presence of an alkali metal hydroxide.
式（２）で表される本発明の化合物は式（３） The compound of the present invention represented by the formula (2) is represented by the formula (3)
（式中、Ｘはハロゲン原子、水酸基、低級アルコキシ基を表す。Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、アリール基のいずれかを表し個々のＲは互いに同一であっても異なっていてもよい。）
で表される化合物とフェノール類とを酸触媒の存在下で縮合反応させることにより得ることができる。
(In the formula, X represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and each R is the same as each other. May be different.)
Can be obtained by subjecting a compound represented by the formula and a phenol to a condensation reaction in the presence of an acid catalyst.
式（３）のＸにおいてハロゲン原子としては塩素原子、臭素原子などが、低級アルキル基としてはメチル基、エチル基、ｔ−ブチル基などが、低級アルコキシ基としてはメトキシ基、エトキシ基などがそれぞれ好ましい基として挙げられる。 In X of the formula (3), a halogen atom is a chlorine atom, a bromine atom, etc., a lower alkyl group is a methyl group, an ethyl group, a t-butyl group, etc., and a lower alkoxy group is a methoxy group, an ethoxy group, etc. It is mentioned as a preferable group.
ここでフェノール類とはフェノール性水酸基を１分子中に１個有する芳香族化合物が挙げられ、その用いうる具体例としては、フェノール、クレゾール、エチルフェノール、ｎ−プロピルフェノール、イソブチルフェノール、ｔ−ブチルフェノール、オクチルフェノール、ノニルフェノール、キシレノール、メチルブチルフェノール、ジ−ｔ−ブチルフェノール等のアルキルフェノールの各種ｏ−、ｍ−、ｐ−異性体、またはビニルフェノール、アリルフェノール、プロペニルフェノール、エチニルフェノールの各種ｏ−、ｍ−、ｐ−異性体、またはシクロペンチルフェノール、シクロヘキシルフェノール、シクロヘキシルクレゾール等のシクロアルキルフェノール、またはフェニルフェノールなどの置換フェノール類が挙げられる。これらのフェノール類は１種類のみを用いてもよく、２種類以上を組み合わせて用いてもよい。 Here, phenols include aromatic compounds having one phenolic hydroxyl group in one molecule, and specific examples that can be used include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol. Various o-, m-, and p-isomers of alkylphenols such as octylphenol, nonylphenol, xylenol, methylbutylphenol, and di-t-butylphenol, or various o-, m- of vinylphenol, allylphenol, propenylphenol, and ethynylphenol , P-isomers, or cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, and cyclohexylresole, or substituted phenols such as phenylphenol. These phenols may be used alone or in combination of two or more.
上記縮合反応を行う場合フェノール類の使用量は式（３）で表される化合物１モルに対して好ましくは０．５〜２０モル、特に好ましくは２〜１５モルである。 When performing the said condensation reaction, the usage-amount of phenols becomes like this. Preferably it is 0.5-20 mol with respect to 1 mol of compounds represented by Formula (3), Most preferably, it is 2-15 mol.
上記縮合反応においては酸触媒を用いるのが好ましく、酸触媒としては種々のものが使用できるが塩酸、硫酸、ｐ−トルエンスルホン酸、シュウ酸等の無機あるいは有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛等のルイス酸などが好ましく、特にｐ−トルエンスルホン酸、硫酸、塩酸が好ましい。これら酸触媒の使用量は特に限定されるものではないが、式（３）で表される化合物の０．１〜３０重量％用いるのが好ましい。 In the above condensation reaction, an acid catalyst is preferably used. Various acid catalysts can be used, but inorganic or organic acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous chloride. Lewis acids such as aluminum and zinc chloride are preferable, and p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are particularly preferable. Although the usage-amount of these acid catalysts is not specifically limited, It is preferable to use 0.1 to 30 weight% of the compound represented by Formula (3).
上記縮合反応は無溶剤下で、あるいは有機溶剤の存在下で行うことができる。有機溶剤を使用する場合の具体例としてはトルエン、キシレン、メチルイソブチルケトンなどが挙げられる。有機溶剤の使用量は仕込んだ原料の総重量に対して５０〜３００重量％が好ましく、特に１００〜２５０重量％が好ましい。反応温度は４０〜１８０℃の範囲が好ましく、反応時間は１〜８時間が好ましい。 The condensation reaction can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. The reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.
反応終了後、洗浄液のｐＨ値が３〜７、好ましくは５〜７になるまで水洗処理を行う。この場合必要により水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属水酸化物、アンモニア、リン酸二水素ナトリウムさらにはジエチレントリアミン、トリエチレンテトラミン、アニリン、フェニレンジアミンなどの有機アミンなど様々な塩基性物質等を中和剤として用いて処理してもよい。水洗処理は常法にしたがって行えばよい。例えば反応混合物中に上記中和剤を溶解した水を加え、分液抽出操作をくり返す。 After completion of the reaction, washing with water is carried out until the pH value of the washing liquid becomes 3 to 7, preferably 5 to 7. In this case, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, and triethylenetetramine as necessary Further, various basic substances such as organic amines such as aniline and phenylenediamine may be used as a neutralizing agent. What is necessary is just to perform a washing process according to a conventional method. For example, water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.
水洗処理を行った後、減圧加熱下で未反応のジヒドロキシベンゼン類及び溶剤を留去し生成物の濃縮を行い、式（２）で表される本発明の化合物を得ることが出来る。 After washing with water, unreacted dihydroxybenzenes and solvent are distilled off under reduced pressure heating to concentrate the product, whereby the compound of the present invention represented by the formula (2) can be obtained.
本発明の化合物からエポキシ樹脂を得る方法としては公知の方法が採用できる。例えば前記で得られた本発明の化合物と過剰のエピクロルヒドリン、エピブロムヒドリン等のエピハロヒドリンとの混合物に水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物をあらかじめ添加し、または添加しながら２０〜１２０℃の温度で１〜１０時間反応させることによりエポキシ樹脂を得ることが出来る。 As a method for obtaining an epoxy resin from the compound of the present invention, a known method can be employed. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to the mixture of the compound of the present invention obtained above and an epihalohydrin such as excess epichlorohydrin or epibromohydrin, or while adding 20 An epoxy resin can be obtained by reacting at a temperature of ˜120 ° C. for 1 to 10 hours.
該エポキシ樹脂を得る反応において、アルカリ金属水酸化物はその水溶液を使用してもよく、その場合は該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に減圧下、または常圧下連続的に水及びエピハロヒドリンを留出させ、更に分液し水は除去しエピハロヒドリンは反応系内に連続的に戻す方法でもよい。 In the reaction for obtaining the epoxy resin, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the reaction is performed under reduced pressure or at normal temperature. A method may be used in which water and epihalohydrin are continuously distilled under pressure, liquid separation is performed, water is removed, and epihalohydrin is continuously returned to the reaction system.
また、本発明の化合物とエピハロヒドリンとの溶解混合物にテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド、等の４級アンモニウム塩を触媒として添加し５０〜１５０℃で１〜５時間反応させて得られる本発明の化合物のハロヒドリンエーテル化物にアルカリ金属水酸化物の固体または水溶液を加え、２０〜１２０℃の温度で１〜１０時間反応させ脱ハロゲン化水素（閉環）させる方法でもよい。 Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added as a catalyst to a dissolved mixture of the compound of the present invention and epihalohydrin and allowed to react at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the compound of the present invention obtained and reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used. .
通常これらの反応において使用されるエピハロヒドリンの量は本発明の化合物の水酸基１当量に対し通常１〜２０モル、好ましくは２〜１０モルである。アルカリ金属水酸化物の使用量は式（２）で表される化合物の水酸基１当量に対し０．８〜１５モル、好ましくは０．９〜１１モルである。また、４級アンモニウム塩の使用量は式（２）の化合物の水酸基１当量に対して、通常１〜１０ｇ、好ましくは２〜８ｇである。更に、反応を円滑に進行させるためにメタノール、エタノールなどのアルコール類の他、ジメチルスルホン、ジメチルスルホキシド等の非プロトン性極性溶媒などを添加して反応を行うことが好ましい。 Usually, the amount of epihalohydrin used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound of the present invention. The usage-amount of an alkali metal hydroxide is 0.8-15 mol with respect to 1 equivalent of hydroxyl groups of a compound represented by Formula (2), Preferably it is 0.9-11 mol. Moreover, the usage-amount of a quaternary ammonium salt is 1-10g normally with respect to 1 equivalent of hydroxyl groups of the compound of Formula (2), Preferably it is 2-8g. Furthermore, in order to make the reaction proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol.
アルコール類を使用する場合、その使用量はエピハロヒドリンの量に対し２〜２０重量％、好ましくは４〜１５重量％である。また非プロトン性極性溶媒を用いる場合はエピハロヒドリンの量に対し５〜１００重量％、好ましくは１０〜９０重量％である。 When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5 to 100 weight% with respect to the quantity of epihalohydrin, Preferably it is 10 to 90 weight%.
これらのエポキシ化反応の反応物を水洗後、または水洗無しに加熱減圧下、１１０〜２５０℃、圧力１０ｍｍＨｇ以下でエピハロヒドリンや添加溶媒などを除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、得られたエポキシ樹脂をトルエン、メチルイソブチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて更に反応を行い、閉環を確実なものにすることもできる。この場合アルカリ金属水酸化物の使用量はエポキシ化に使用した本発明の化合物の水酸基１当量に対して好ましくは０．０１〜０．３モル、特に好ましくは０．０５〜０．２モルである。反応温度は５０〜１２０℃、反応時間は通常０．５〜２時間である。 After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin, added solvent, and the like are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to make an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. In addition, further reactions can be performed to ensure ring closure. In this case, the amount of alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 0.2 mol, relative to 1 equivalent of the hydroxyl group of the compound of the present invention used for epoxidation. is there. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することによりエポキシ樹脂が得られる。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and an epoxy resin is obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.
こうして得られた式（１）で表されるエポキシ樹脂は、硬化剤、必要により硬化促進剤等と均一に混合しエポキシ樹脂組成物とすることができる。このエポキシ樹脂組成物において、エポキシ樹脂として式（１）のエポキシ樹脂以外のエポキシ樹脂を併用することも可能である。他のエポキシ樹脂を併用する場合、全エポキシ樹脂中の式（１）のエポキシ樹脂の占める割合は、２０重量％以上が好ましい。式（１）のエポキシ樹脂を含有するエポキシ樹脂組成物において、硬化剤としてはアミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物などが使用できる。用いうる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、フェノ−ルノボラック、及びこれらの変性物、イミダゾ−ル、ＢＦ3 −アミン錯体、グアニジン誘導体などが挙げられる。また式（１）のエポキシ樹脂の原料として用いた本発明の化合物も硬化剤として用いることが出来る。これらの硬化剤はそれぞれ単独で用いてもよいし、２種以上組み合わせて用いてもよい。 The epoxy resin represented by the formula (1) thus obtained can be uniformly mixed with a curing agent and, if necessary, a curing accelerator and the like to obtain an epoxy resin composition. In this epoxy resin composition, an epoxy resin other than the epoxy resin of the formula (1) can be used in combination as the epoxy resin. When other epoxy resins are used in combination, the proportion of the epoxy resin of the formula (1) in all epoxy resins is preferably 20% by weight or more. In the epoxy resin composition containing the epoxy resin of the formula (1), an amine compound, an acid anhydride compound, an amide compound, a phenol compound, or the like can be used as the curing agent. 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. Merit acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, and modified products thereof, Examples include imidazole, BF 3 -amine complex, and guanidine derivatives. Moreover, the compound of this invention used as a raw material of the epoxy resin of Formula (1) can also be used as a hardening | curing agent. These curing agents may be used alone or in combination of two or more.
これらの硬化剤の使用量は、エポキシ樹脂のエポキシ基１当量に対して０．７〜１．２当量が好ましい。エポキシ基１当量に対して、０．７当量に満たない場合、あるいは１．２当量を超える場合、いずれも硬化が不完全となり良好な硬化物性が得られない恐れがある。 The amount of these curing agents used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
また上記硬化剤を用いる際に硬化促進剤を併用しても差し支えない。用いうる硬化促進剤の具体例としては２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾ−ル類、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズなどの金属化合物などが挙げられる。硬化促進剤は、エポキシ樹脂１００重量部に対して０．１〜５．０重量部が必要に応じ用いられる。さらに、このエポキシ樹脂組成物には、必要に応じてシリカ、アルミナ、タルク等の充填材やシランカップリング剤、離型剤、顔料等の種々の配合剤を添加することができる。 Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin. Furthermore, various compounding agents, such as fillers, such as a silica, an alumina, and a talc, a silane coupling agent, a mold release agent, and a pigment, can be added to this epoxy resin composition as needed.
式（１）のエポキシ樹脂を含有するエポキシ樹脂組成物は、各成分を均一に混合することにより得られる。該エポキシ樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えば式（１）のエポキシ樹脂と硬化剤、充填剤及びその他の添加剤とを必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合して本発明のエポキシ樹脂組成物を得、そのエポキシ樹脂組成物を溶融後注型あるいはトランスファー成形機などを用いて成形し、さらに８０〜２００℃で２〜１０時間に加熱することにより硬化物を得ることができる。 The epoxy resin composition containing the epoxy resin of Formula (1) is obtained by mixing each component uniformly. The epoxy resin composition can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the formula (1) and a curing agent, a filler, and other additives are mixed thoroughly as necessary using an extruder, a kneader, a roll, or the like, as necessary. An epoxy resin composition can be obtained, and the epoxy resin composition can be melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product. it can.
また該エポキシ樹脂組成物をトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン等の溶剤に溶解させ、ガラス繊維、カ−ボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させ加熱乾燥して得たプリプレグを熱プレス成形して硬化物を得ることもできる。 Also, the epoxy resin composition is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and impregnated on a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and the like. A prepreg obtained by heating and drying can be subjected to hot press molding to obtain a cured product.
この際の希釈溶剤は該エポキシ樹脂組成物と該希釈溶剤の混合物中で通常１０〜７０重量％、好ましくは１５〜６５重量％を占める量を使用する。 The dilution solvent used here is usually 10 to 70% by weight, preferably 15 to 65% by weight in the mixture of the epoxy resin composition and the dilution solvent.
こうして得られる硬化物は耐熱性、耐水性及び機械的強度に優れているため、耐熱性、耐水性の要求される広範な分野で用いることができる。具体的には封止材料、積層板、絶縁材料などのあらゆる電気・電子材料として有用である。また、成型材料、接着剤、塗料などの分野にも用いることができる。 Since the cured product thus obtained is excellent in heat resistance, water resistance and mechanical strength, it can be used in a wide range of fields requiring heat resistance and water resistance. Specifically, it is useful as any electrical / electronic material such as a sealing material, a laminate, and an insulating material. It can also be used in fields such as molding materials, adhesives and paints.
次に本発明を実施例、比較例により更に具体的に説明するが、以下において部は特に断わりのない限り重量部を意味する。 Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, parts means parts by weight unless otherwise specified.
実施例１
温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに、下記式（４）
Example 1
In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, the following formula (4)
で表される化合物２４２部、フェノール２８２部を仕込み、室温下、窒素を吹き込みながら撹拌した。ｐ−トルエンスルホン酸（１水和物）２．８部を発熱に注意しながら液温が５０℃を超えないようにゆっくり添加した。その後油浴中で１１０℃まで加熱し、２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１０００ｍｌを加え、分液ロートに移し水洗した。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物を加熱減圧下に除去し、軟化点が１０８℃の樹脂状化合物（本発明の化合物）２９９部を得た。この化合物について溶媒にテトラヒドロフランを用いてＧＰＣ分析、マススペクトル（ＦＡＢ−ＭＳ）分析によって分析した結果、この化合物は下記式（５） 242 parts of a compound represented by the above and 282 parts of phenol were charged and stirred at room temperature while blowing nitrogen. 2.8 parts of p-toluenesulfonic acid (monohydrate) was slowly added so that the liquid temperature did not exceed 50 ° C. while paying attention to heat generation. Then, it heated to 110 degreeC in the oil bath, and was made to react for 2 hours. After completion of the reaction, 1000 ml of methyl isobutyl ketone was further added, transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, the solvent and unreacted substances were removed from the organic layer under heating and reduced pressure to obtain 299 parts of a resinous compound (compound of the present invention) having a softening point of 108 ° C. This compound was analyzed by GPC analysis and mass spectrum (FAB-MS) analysis using tetrahydrofuran as a solvent. As a result, the compound was represented by the following formula (5).
で表される化合物であることが確認された。ＧＰＣ分析の結果から水酸基当量を算出すると２２８ｇ／ｅｑとなった。またｎの平均値は２．１であった。 It was confirmed that it is a compound represented by. The hydroxyl equivalent calculated from the results of GPC analysis was 228 g / eq. The average value of n was 2.1.
参考例１
温度計、冷却管、撹拌機を取り付けたフラスコに窒素ガスパージを施しながら実施例１で得られた化合物２２８部、エピクロルヒドリン３７０部、ジメチルスルホキシド９２．５部を仕込み溶解させた。更に５０℃に加熱しフレーク状水酸化ナトリウム（純分９９％）４０．４部を９０分かけて分割添加し、その後更に６０℃で２時間、７０℃で１時間反応させた。反応終了後、１３０℃で加熱減圧下ジメチルスルホキシド及びエピクロルヒドリンを留去し、残留物に５６８部のメチルイソブチルケトンを加え溶解した。
Reference example 1
A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen gas, and 228 parts of the compound obtained in Example 1, 370 parts of epichlorohydrin, and 92.5 parts of dimethyl sulfoxide were charged and dissolved. The mixture was further heated to 50 ° C., and 40.4 parts of flaky sodium hydroxide (pure 99%) were added in portions over 90 minutes, and then reacted at 60 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, dimethyl sulfoxide and epichlorohydrin were distilled off at 130 ° C. under reduced pressure by heating, and 568 parts of methyl isobutyl ketone was added to the residue and dissolved.
更にこのメチルイソブチルケトンの溶液を７０℃に加熱し３０重量％の水酸化ナトリウム水溶液１０部を添加し１時間反応させた後、水洗を３回繰り返しｐＨを中性とした。更に水層は分離除去し、ロータリエバポレーターを使用して油層から加熱減圧下メチルイソブチルケトンを留去し、下記式（６） Further, this methyl isobutyl ketone solution was heated to 70 ° C., 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water three times to neutralize the pH. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer using a rotary evaporator under heating and reduced pressure.
（式中、Ｇはグリシジル基を表し、ｎの平均値は２．１である。）で表されるエポキシ樹脂（Ａ）２６７部を得た。得られたエポキシ樹脂の軟化点は８５．３℃、エポキシ当量は２９５ｇ／ｅｑであった。 (In the formula, G represents a glycidyl group, and the average value of n is 2.1.) 267 parts of an epoxy resin (A) represented by the following formula was obtained. The resulting epoxy resin had a softening point of 85.3 ° C. and an epoxy equivalent of 295 g / eq.
実施例２
フェノールの代わりにｏ−クレゾール４３２部を用いた以外は実施例１と同様に反応を行い軟化点が１０１．５℃の樹脂状化合物（本発明の化合物）３３７部を得た。この化合物について溶媒にテトラヒドロフランを用いてＧＰＣ分析、マススペクトル（ＦＡＢ−ＭＳ）分析によって分析した結果、この化合物は下記式（７）
Example 2
A reaction was carried out in the same manner as in Example 1 except that 432 parts of o-cresol was used instead of phenol to obtain 337 parts of a resinous compound (compound of the present invention) having a softening point of 101.5 ° C. This compound was analyzed by GPC analysis and mass spectrum (FAB-MS) analysis using tetrahydrofuran as a solvent. As a result, the compound was represented by the following formula (7).
で表される化合物であることが確認された。ＧＰＣ分析の結果から水酸基当量を算出すると２２９ｇ／ｅｑとなった。またｎの平均値は１．１であった。 It was confirmed that it is a compound represented by. The hydroxyl equivalent calculated from the results of GPC analysis was 229 g / eq. The average value of n was 1.1.
参考例２
前記式（７）で表される化合物２２９部を用いた以外は参考例１と同様にエポキシ化反応を行い下記式（８）
Reference example 2
An epoxidation reaction was performed in the same manner as in Reference Example 1 except that 229 parts of the compound represented by the formula (7) were used.
（式中、Ｇはグリシジル基を表し、ｎの平均値は１．１である。）で表される本発明のエポキシ樹脂（Ｂ）２７３部を得た。得られたエポキシ樹脂の軟化点は８２．２℃、エポキシ当量は２９３ｇ／ｅｑであった。 (In the formula, G represents a glycidyl group, and the average value of n is 1.1.) 273 parts of the epoxy resin (B) of the present invention represented by the following formula was obtained. The resulting epoxy resin had a softening point of 82.2 ° C. and an epoxy equivalent of 293 g / eq.
比較例１
特許文献１の実施例１に従い下記式（９）
Comparative Example 1
According to Example 1 of Patent Document 1, the following formula (9)
で示される化合物を得た。 The compound shown by these was obtained.
次いで式（９）の化合物を用いて同公報実施例２に従いエポキシ樹脂（Ｃ）を得た。 Subsequently, the epoxy resin (C) was obtained according to Example 2 of the publication using the compound of the formula (9).
参考例３〜４、比較例２
参考例１、２で得られたエポキシ樹脂（Ａ）、（Ｂ）、比較用の前記エポキシ樹脂（Ｃ）、硬化剤としてフェノールノボラック（水酸基当量１０６ｇ／ｅｑ、軟化点８０．２℃）、硬化促進剤としてトリフェニルホスフィン（ＴＰＰ）を用い、表１の配合物の組成の欄に示す組成で配合して、７０℃で１５分ロールで混練し、１５０℃、成形圧力５０ｋｇ／ｃｍ2 で１８０秒間トランスファー成形して、その後１６０℃で２時間、更に１８０℃で８時間硬化せしめて試験片を作成し、ガラス転移点、吸水率を測定した。結果を表１に示す。尚、ガラス転移点、吸水率及び曲げ強度の測定条件は次の通りである。また、表中、配合物の組成の欄の数値は重量部を示す。
Reference Examples 3-4, Comparative Example 2
Epoxy resins (A) and (B) obtained in Reference Examples 1 and 2, the comparative epoxy resin (C), a phenol novolak (hydroxyl equivalent: 106 g / eq, softening point: 80.2 ° C.) as a curing agent, curing Using triphenylphosphine (TPP) as an accelerator, blended with the composition shown in the composition column of Table 1, kneaded with a roll at 70 ° C. for 15 minutes, 150 ° C., and molding pressure of 50 kg / cm 2 at 180 ° C. The sample was transfer molded for 2 seconds, then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to prepare a test piece, and the glass transition point and water absorption were measured. The results are shown in Table 1. In addition, the measurement conditions of a glass transition point, a water absorption rate, and bending strength are as follows. Moreover, the numerical value of the column of the composition of a compound in a table | surface shows a weight part.
ガラス転移点熱機械測定装置（ＴＭＡ）
：真空理工（株）製 ＴＭ−７０００
昇温速度：２℃／ｍｉｎ
吸水率
試験片（硬化物）：直径５０ｍｍ厚さ３ｍｍ 円盤１００℃の水中で２４時間煮沸した後の重量増加率（％）
曲げ強度
ＪＩＳ Ｋ−６９１１に準拠し測定
Glass transition point thermomechanical measurement system (TMA)
: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C / min
Water absorption rate Test piece (cured product): Diameter 50 mm, thickness 3 mm, disk weight increase rate after boiling for 24 hours in 100 ° C. water (%)
Bending strength Measured according to JIS K-6911
表１より本発明の化合物を原料とするエポキシ樹脂の硬化物は、公知のビフェニル骨格を有するエポキシ樹脂の硬化物に較べ、高いガラス転移点、低い吸水率及び、高い機械強度を示した。 From Table 1, the cured product of the epoxy resin using the compound of the present invention as a raw material exhibited a high glass transition point, a low water absorption, and a high mechanical strength as compared with a cured product of an epoxy resin having a known biphenyl skeleton.
Claims (1)
で表される化合物。 Following formula (2)
A compound represented by
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