JP2007112958A - Phenol resin, method for producing the same, epoxy resin, and application thereof - Google Patents
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Abstract
Description
本発明は、溶融粘度の低い結晶性エポキシ樹脂の原料として有用なフェノール樹脂、結晶性エポキシ樹脂、該エポキシ樹脂を含有するエポキシ樹脂組成物、およびその硬化物に関する。 The present invention relates to a phenol resin useful as a raw material for a crystalline epoxy resin having a low melt viscosity, a crystalline epoxy resin, an epoxy resin composition containing the epoxy resin, and a cured product thereof.
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、電気的性質などに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。半導体封止材などの用途においては耐熱性が要求されるためクレゾールノボラック型エポキシ樹脂が広く利用されている。実装方式は、表面実装方式が一般的になり、半導体パッケージも半田リフロー時に直接高温に晒されることが多くなった上、近年の環境問題に対する意識の向上につれ、半導体を実装する際に鉛フリー半田を使用する場合が増えている。鉛フリー半田は従来の半田と比較して溶融温度が約２０℃高い（約２６０℃）ため、半田リフロー時にパッケージクラックが生じる可能性は従来の半導体封止材よりもはるかに高くなった。そのような背景において、耐熱性、耐湿性、耐衝撃性等の諸特性に優れた性能を有するエポキシ樹脂として、ビフェニルノボラック型のエポキシ樹脂が提案されている（特許文献１参照）。また、ビフェニル骨格を含むエポキシ樹脂の低溶融粘度化として分子量分布を有しない結晶性エポキシ樹脂が提案されている（特許文献２参照）。また、結晶性エポキシ樹脂に有用な原料となるビフェニル骨格を有するフェノール化合物については既に提案されているが、その原料として使用されるフェノール類についてはフェノールの他にクレゾールやキシレノールのような１から２置換のフェノール類が記載されている（特許文献３）。 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, moldings It is used in a wide range of fields such as materials and casting materials. In applications such as semiconductor encapsulants, cresol novolac epoxy resins are widely used because heat resistance is required. As the mounting method, the surface mounting method has become common, and semiconductor packages are often directly exposed to high temperatures during solder reflow. In addition, as the awareness of environmental issues has increased in recent years, lead-free solder has been used when mounting semiconductors. The use of is increasing. Since lead-free solder has a melting temperature about 20 ° C. higher than that of conventional solder (about 260 ° C.), the possibility of package cracks during solder reflow is much higher than that of conventional semiconductor encapsulants. In such a background, a biphenyl novolac type epoxy resin has been proposed as an epoxy resin having excellent performance such as heat resistance, moisture resistance and impact resistance (see Patent Document 1). Further, a crystalline epoxy resin having no molecular weight distribution has been proposed as a low melt viscosity of an epoxy resin containing a biphenyl skeleton (see Patent Document 2). Moreover, although the phenol compound which has a biphenyl skeleton used as a raw material useful for a crystalline epoxy resin has already been proposed, the phenols used as the raw material are 1 to 2 such as cresol and xylenol in addition to phenol. Substituted phenols are described (Patent Document 3).
特許文献１の実施例に記載されているような分子量分布を有するノボラック型のエポキシ樹脂は、溶融粘度が比較的高いため高フィラー充填には限界があった。また、特許文献２に記載の結晶性エポキシ樹脂を製造するためには、樹脂状のフェノール樹脂から晶析工程を経て得られる結晶状のフェノール樹脂を使用する必要があり（[００１８]）、工業的に安価に製造することが難しい。本発明の主たる目的は、再結晶工程を経なくても製造が可能であり、しかもその硬化物において耐熱性、耐湿性、耐衝撃性に優れたビフェニル骨格を有する結晶性エポキシ樹脂を提供することにある。 The novolac type epoxy resin having a molecular weight distribution as described in the examples of Patent Document 1 has a limit in filling with a high filler because of its relatively high melt viscosity. In addition, in order to produce the crystalline epoxy resin described in Patent Document 2, it is necessary to use a crystalline phenol resin obtained from a resinous phenol resin through a crystallization step ([0018]). It is difficult to manufacture inexpensively. The main object of the present invention is to provide a crystalline epoxy resin that can be produced without going through a recrystallization step and that has a biphenyl skeleton excellent in heat resistance, moisture resistance, and impact resistance in the cured product. It is in.
本発明者は、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventor has completed the present invention.
即ち、本発明は
（１）フェノールアラルキル型樹脂であって、下記式（１）で表される化合物を主成分とするフェノール樹脂、
That is, the present invention is (1) a phenol aralkyl type resin, the phenol resin mainly comprising a compound represented by the following formula (1),
（２）下記式（２）で表されるビフェニル化合物１モルに対しｐ−クレゾール１０〜３０モルを反応させることを特徴とする、上記（１）記載のフェノール樹脂の製造法、 (2) A method for producing a phenol resin as described in (1) above, wherein 10 to 30 mol of p-cresol is reacted with 1 mol of a biphenyl compound represented by the following formula (2):
（式（２）において、Ｘは塩素原子、臭素原子、メトキシ基、エトキシ基または水酸基を表す。）
（３）上記（１）記載のフェノール樹脂をエピハロヒドリンとアルカリ金属水酸化物の存在下、反応させることにより得られる下記式（３）で表される化合物を主成分とする結晶性エポキシ樹脂、
(In Formula (2), X represents a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group.)
(3) A crystalline epoxy resin containing as a main component a compound represented by the following formula (3) obtained by reacting the phenol resin described in (1) in the presence of epihalohydrin and an alkali metal hydroxide,
（４）上記（３）に記載のエポキシ樹脂及び硬化剤を含有することを特徴とするエポキシ樹脂組成物、
（５）硬化促進剤を含有する上記（４）に記載のエポキシ樹脂組成物、
（６）無機充填剤を含有する上記（４）または（５）に記載のエポキシ樹脂組成物、
（７）上記（４）、（５）または（６）のいずれか１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。
(4) An epoxy resin composition comprising the epoxy resin according to (3) and a curing agent,
(5) The epoxy resin composition according to the above (4), which contains a curing accelerator,
(6) The epoxy resin composition according to the above (4) or (5), which contains an inorganic filler,
(7) The present invention relates to a cured product obtained by curing the epoxy resin composition according to any one of (4), (5), and (6).
本発明のエポキシ樹脂はこれまでに提案されてきたエポキシ樹脂と比較して、耐熱性、耐湿性、流動性などのバランスに優れた硬化物を与える。従って、本発明のエポキシ樹脂組成物は電気・電子材料、成型材料、注型材料、積層材料、塗料、接着剤、レジスト、光学材料などの広範囲の用途にきわめて有用である。 The epoxy resin of this invention gives the hardened | cured material excellent in balance, such as heat resistance, moisture resistance, and fluidity, compared with the epoxy resin proposed so far. Therefore, the epoxy resin composition of the present invention is extremely useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, optical materials and the like.
本発明のフェノール樹脂は、ｐ−クレゾールと下記式（２） The phenol resin of the present invention comprises p-cresol and the following formula (2)
（上記式（２）において、Ｘは塩素原子、臭素原子、メトキシ基、エトキシ基または水酸基を表す。）で表されるビフェニル化合物とを縮合反応させた後、未反応のｐ−クレゾール、および不純物を加熱除去することで得られ、下記式（１）で表される化合物をその主成分（通常ＨＰＬＣ測定による面積％で５０面積％以上）とし、他の成分として、式（２）の化合物とｐ−クレゾールの結合単位が３個以上の高分子量化合物を少量含む樹脂である。本発明のエポキシ樹脂は、このフェノール樹脂をグリシジルエーテル化することで得られる。 (In the above formula (2), X represents a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, or a hydroxyl group.) After a condensation reaction with a biphenyl compound represented by the following formula, unreacted p-cresol and impurities The compound represented by the following formula (1) is obtained as a main component (usually 50 area% or more by area% by HPLC measurement), and the other compound is a compound represented by the following formula (1): It is a resin containing a small amount of a high molecular weight compound having 3 or more p-cresol bonding units. The epoxy resin of the present invention can be obtained by glycidyl etherifying this phenol resin.
本発明においては、フェノール類としてｐ−クレゾールを用いることに特徴がある。すなわち、上記縮合反応によって得られるフェノール樹脂は、ｐ−クレゾールの代わりにフェノール、ｏ−クレゾール、ｍ−クレゾールを用いた場合と異なり、式（１）で表されるように基本的に配位異性体を含まない。そして、一つの骨格が主成分となるが故に、式（１）を主成分とするフェノール樹脂をグリシジルエーテル化した本発明のエポキシ樹脂は結晶性を有する。 The present invention is characterized by using p-cresol as a phenol. That is, the phenol resin obtained by the above condensation reaction is different from the case of using phenol, o-cresol, and m-cresol instead of p-cresol, basically as shown by the formula (1). Does not include body. And since one frame | skeleton becomes a main component, the epoxy resin of this invention which made glycidyl ether the phenol resin which has Formula (1) as a main component has crystallinity.
上記の縮合反応において、原料の仕込み比率は、式（２）の化合物１モルに対してｐ−クレゾールが通常１０〜３０モル、好ましくは１５〜２５モルである。 In the above condensation reaction, the charging ratio of the raw material is usually 10 to 30 mol, preferably 15 to 25 mol, of p-cresol with respect to 1 mol of the compound of the formula (2).
式（２）の化合物としては例えば、４，４’−ビス（クロロメチル）−１，１’−ビフェニル、４，４’−ビス（ブロモメチル）−１，１’−ビフェニル、４，４’−ビス（メトキシメチル）−１，１’−ビフェニル、４，４’−ビス（エトキシメチル）−１，１’−ビフェニルなどが挙げられる。 Examples of the compound of the formula (2) include 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (bromomethyl) -1,1′-biphenyl, 4,4′- Bis (methoxymethyl) -1,1′-biphenyl, 4,4′-bis (ethoxymethyl) -1,1′-biphenyl and the like can be mentioned.
反応時に必要に応じて酸触媒を添加することができる。具体的には、種々のものが使用できるが硫酸、ｐ−トルエンスルホン酸、シュウ酸等の有機あるいは無機酸、塩化第二錫、塩化亜鉛、塩化第二鉄等のフリーデルクラフツ型触媒等が挙げられる。なかでも塩化第二錫、硫酸、ｐ−トルエンスルホン酸が好ましい。これら酸触媒の使用量は触媒の種類により異なるが、式（２）の化合物に対して０．０００５〜５重量％の範囲内で添加すれば良い。 An acid catalyst can be added as needed during the reaction. Specific examples include various organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, and oxalic acid, Friedel-Crafts type catalysts such as stannic chloride, zinc chloride, and ferric chloride. Can be mentioned. Of these, stannic chloride, sulfuric acid, and p-toluenesulfonic acid are preferable. The amount of the acid catalyst used varies depending on the type of the catalyst, but it may be added in the range of 0.0005 to 5% by weight with respect to the compound of the formula (2).
縮合反応は無溶剤下でも溶剤の存在下でも行うことが出来る。溶剤を使用する場合、用い得る溶剤としてはメタノール、エタノール、イソプロパノール、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン等が挙げられる。溶剤の使用量としてはｐ−クレゾールと式（２）で表される化合物の合計重量に対して通常１０〜３００重量％、好ましくは２０〜２５０重量％である。縮合反応温度としては通常４０〜１５０℃、反応時間としては通常１〜１０時間である。 The condensation reaction can be performed in the absence of a solvent or in the presence of a solvent. When a solvent is used, examples of the solvent that can be used include methanol, ethanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene. The amount of the solvent used is usually 10 to 300% by weight, preferably 20 to 250% by weight, based on the total weight of p-cresol and the compound represented by formula (2). The condensation reaction temperature is usually 40 to 150 ° C., and the reaction time is usually 1 to 10 hours.
縮合反応終了後、中和、水洗などにより酸触媒を除去し、次いで加熱減圧下で必要により使用した溶剤及び未反応のｐ−クレゾールを除去する。必要により再結晶などの精製を行うことも可能であるが、コスト面で不利となる。再結晶に使用できる溶剤としてはトルエン、メチルエチルケトン、アセトン、メチルイソブチルケトン、ｎ−ヘキサン、メタノール、エタノール等が挙げられるが、これらに限定されるものではなく、各種溶剤を混合しても構わない。再結晶は、これら溶剤を加熱し、反応混合物を溶解した後、冷却、ろ過を行う。 After completion of the condensation reaction, the acid catalyst is removed by neutralization, washing with water, etc., and then the solvent used and unreacted p-cresol are removed as necessary under heating and reduced pressure. Although purification such as recrystallization can be performed if necessary, it is disadvantageous in terms of cost. Solvents that can be used for recrystallization include toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, n-hexane, methanol, ethanol, and the like, but are not limited thereto, and various solvents may be mixed. In recrystallization, these solvents are heated to dissolve the reaction mixture, and then cooled and filtered.
こうして得られた本発明のフェノール樹脂をエピハロヒドリン中でアルカリ金属水酸化物の存在下、グリシジルエーテル化することにより下記式（３）で表される化合物を主成分とする本発明のエポキシ樹脂を得ることができる。本発明の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。 The thus obtained phenol resin of the present invention is glycidyl etherified in the presence of an alkali metal hydroxide in an epihalohydrin to obtain the epoxy resin of the present invention mainly comprising a compound represented by the following formula (3). be able to. In the reaction for obtaining the epoxy resin of the present invention, 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 under reduced pressure. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, removal of water, and epihalohydrin being continuously returned to the reaction system.
また本発明のフェノール樹脂とエピハロヒドリンの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０．５〜８時間反応させて得られるフェノール樹脂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℃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 or trimethylbenzylammonium chloride is added as a catalyst to the mixture of the phenolic resin and epihalohydrin of the present invention and reacted at 50 to 150 ° C. for 0.5 to 8 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of a phenol resin and reacting at 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フェノール樹脂の水酸基１モルに対し通常０．８〜１２モル、好ましくは０．９〜１１モルである。この際、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、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 0.8 to 12 mol, preferably 0.9 to 11 mol, based on 1 mol of the hydroxyl group of the phenol resin of the present invention. In this case, it is preferable to carry out the reaction by adding an alcohol such as methanol or ethanol, an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide, etc. in order to make the reaction proceed smoothly.
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通常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通常５〜１５０重量％、好ましくは１０〜１４０重量％である。 When using alcohol, the amount of its use is 2-20 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 4-15 weight%. Moreover, when using an aprotic polar solvent, it is 5-150 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-140 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でエピハロヒドリンや溶媒等を除去する。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、回収し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反応を行い、閉環を確実なものにすることも出来る。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式（１）中の水酸基１当量に対して通常０．０１〜０．３モル、好ましくは０．０５〜０．２モルである。反応温度は通常５０〜１２０℃、反応時間は通常０．５〜２時間である。
反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂が得られる。
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. In order to make the epoxy resin less hydrolyzable halogen, the recovered 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 added. The reaction can be carried out to ensure the 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, relative to 1 equivalent of the hydroxyl group in the formula (1) used for epoxidation. . 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 of the present invention.
なお、必要により得られたエポキシ樹脂に結晶化を促進させる処理、または再結晶処理を施してもよい。結晶化を促進させる処理とは、樹脂にせん断を加える方法、種結晶を用いる方法などが挙げられる。再結晶処理において、再結晶に使用できる溶剤としてはトルエン、メチルエチルケトン、アセトン、メチルイソブチルケトン、ｎ−ヘキサン、メタノール、エタノール等が挙げられるが、これらに限定されるものではなく、各種溶剤を混合しても構わない。再結晶は、これら溶剤を加熱し、反応混合物を溶解した後、冷却、ろ過を行うといった通常の方法で支障はない。 In addition, you may perform the process which accelerates | stimulates crystallization, or the recrystallization process to the obtained epoxy resin as needed. Examples of the treatment for promoting crystallization include a method of applying shear to the resin and a method of using a seed crystal. In the recrystallization process, toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, n-hexane, methanol, ethanol and the like can be used as a solvent that can be used for recrystallization. It doesn't matter. Recrystallization has no problem in the usual method of heating these solvents and dissolving the reaction mixture, followed by cooling and filtration.
以下、本発明のエポキシ樹脂組成物について説明する。本発明のエポキシ樹脂は単独でまたは他のエポキシ樹脂と併用して使用することが出来る。併用する場合、本発明のエポキシ樹脂の全エポキシ樹脂中に占める割合は３０重量％以上が好ましく、特に４０重量％以上が好ましい。 Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
本発明のエポキシ樹脂と併用し得る他のエポキシ樹脂の具体例としては、オルソクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ナフトール型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビスフェノール型エポキシ樹脂、その他一般の公知のエポキシ樹脂などが挙げられるがこれらは単独で用いてもよく、２種以上併用してもよい。 Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include orthocresol novolac type epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, trisphenol methane type epoxy resins, naphthol type epoxy resins, phenol aralkyl types. Examples include epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, hydroquinone type epoxy resins, bisphenol type epoxy resins, and other general known epoxy resins. These may be used alone or in combination of two or more. Also good.
本発明のエポキシ樹脂組成物は硬化剤を含有する。使用できる硬化剤としては、フェノール系化合物の他にアミン系化合物、酸無水物系化合物、アミド系化合物などが挙げられるが、これらに限定されるものではない。用い得る硬化剤の具体例としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、トリフェノールメタン型樹脂、フェニレンまたはビフェニレン骨格を含むフェノールアラルキル樹脂、本発明のフェノール化合物、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がこれらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。 The epoxy resin composition of the present invention contains a curing agent. Examples of the curing agent that can be used include, but are not limited to, amine compounds, acid anhydride compounds, amide compounds, and the like in addition to phenol compounds. Specific examples of the curing agent that can be used include phenol novolac resin, cresol novolac resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, triphenolmethane type resin, phenol aralkyl resin containing phenylene or biphenylene skeleton, and phenol of the present invention. Compound, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro B phthalic anhydride, phenol - novolac, and modified products thereof, imidazo - Le, BF 3 - amine complex, but such guanidine derivatives are not limited thereto. These may be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物において硬化剤の使用量は、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。 In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent 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.
また本発明のエポキシ樹脂組成物においては硬化促進剤を併用しても差し支えない。用い得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、オクチル酸スズ等の金属化合物等が挙げられる。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。 In the epoxy resin composition of the present invention, a curing accelerator may be used in combination. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- 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.
本発明のエポキシ樹脂組成物は必要により無機充填剤を含有しうる。用いうる無機充填剤の具体例としてはシリカ、アルミナ、タルク等が挙げられる。無機充填剤は本発明のエポキシ樹脂組成物中において０〜９０重量％を占める量が用いられる。更に本発明のエポキシ樹脂組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、顔料等の種々の配合剤を添加することができる。 The epoxy resin composition of the present invention may contain an inorganic filler as necessary. Specific examples of the inorganic filler that can be used include silica, alumina, talc and the like. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention. Furthermore, various compounding agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and pigments can be added to the epoxy resin composition of the present invention.
本発明のエポキシ樹脂組成物は必要によりエポキシ樹脂以外の熱硬化性樹脂、または熱可塑性樹脂を含有しうる。具体例としてはビニルエステル樹脂、不飽和ポリエステル樹脂、マレイミド樹脂、ポリシアナート樹脂、イソシアナート化合物、ベンゾオキサジン化合物、ビニルベンジルエーテル化合物、ポリブタジエンおよびこの変性物、アクリロニトリル共重合体の変性物、インデン樹脂、フッ素樹脂、シリコーン樹脂、ポリエーテルイミド、ポリエーテルスルホン、ポリフェニレンエーテル、ポリアセタール、ポリスチレン、ポリエチレン、ジシクロペンタジエン樹脂等が挙げられる。熱硬化性樹脂、または熱可塑性樹脂は本発明のエポキシ樹脂組成物中において０〜９０重量％を占める量が用いられる。 The epoxy resin composition of the present invention may contain a thermosetting resin other than an epoxy resin, or a thermoplastic resin, if necessary. Specific examples include vinyl ester resins, unsaturated polyester resins, maleimide resins, isocyanate resins, isocyanate compounds, benzoxazine compounds, vinyl benzyl ether compounds, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, indene resins, fluorine Examples thereof include resins, silicone resins, polyether imides, polyether sulfones, polyphenylene ethers, polyacetals, polystyrenes, polyethylenes, and dicyclopentadiene resins. The thermosetting resin or thermoplastic resin is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention.
本発明のエポキシ樹脂組成物は、前記の各成分を均一に混合することにより得られる。本発明の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。例えばエポキシ樹脂、硬化剤並びに必要により硬化促進剤、無機充填剤及び配合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型機などを用いて成型し、さらに８０〜２００℃で２〜１０時間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 of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin, a curing agent and, if necessary, a curing accelerator, an inorganic filler, and a compounding agent are thoroughly mixed using an extruder, a kneader, a roll, etc., as necessary, until they are uniform, and then an epoxy resin. A cured product can be obtained by obtaining a composition, molding the epoxy resin composition after casting using a casting or transfer molding machine, and heating at 80 to 200 ° C. for 2 to 10 hours.
また本発明の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半乾燥して得たプリプレグを熱プレス成型して硬化物を得ることもできる。この際の溶剤は、本発明のエポキシ樹脂組成物と該溶剤の混合物中で通常１０〜７０重量％、好ましくは１５〜７０重量％を占める量を用いる。 In addition, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and is applied to a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnation and heating and semi-drying can be subjected to hot press molding to obtain a cured product. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
次に本発明を実施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である。なお、軟化点、ＨＰＬＣ、エポキシ当量、融点、溶融粘度、ＧＰＣは以下の条件で測定した。 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 softening point, HPLC, epoxy equivalent, melting point, melt viscosity, and GPC were measured under the following conditions.
・軟化点
ＪＩＳ Ｋ−７２３４に記載の方法で測定した。
・ＨＰＬＣ
カラム；Ｉｎｅｒｔｓｉｌ ＯＤＳ−２（４．６ｍｍ×１５０ｍｍ）
（ジーエル サイエンス（株）製）
カラム温度；４０℃
溶離液：水／アセトニトリル
グラジエント：３０％（アセトニトリル）→１００％（２８分／グラジエント）
流速：１ｍｌ／ｍｉｎ．
検出：ＵＶ（２７４ｎｍ）
・エポキシ当量
ＪＩＳ Ｋ−７２３６に記載の方法で測定した。
・融点：ＤＳＣ法
測定機械；示差走査熱量測定（ＤＳＣ６２００ セイコー電子工業（株））
昇温速度；１０℃／ｍｉｎ．
パン；Ａｌパン
・溶融粘度
１５０℃におけるコーンプレート法における溶融粘度
測定器械：コーンプレート（ＩＣＩ）高温粘度計
（RESEACH EQUIPMENT(LONDON)LTD.製）
コーンＮｏ．：３（測定範囲０〜２．００Pa・s）
試料量：０．１５±０．０１ｇ
・ＧＰＣ
カラム：GPC KF-803＋GPC KF-802.5＋GPC KF-802＋GPC KF-801
（昭和電工（株）製）
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：１ｍｌ／ｍｉｎ．
検出：ＲＩ
-Softening point Measured by the method described in JIS K-7234.
・ HPLC
Column; Inertsil ODS-2 (4.6 mm × 150 mm)
(Manufactured by GL Sciences)
Column temperature: 40 ° C
Eluent: Water / acetonitrile Gradient: 30% (acetonitrile) → 100% (28 minutes / gradient)
Flow rate: 1 ml / min.
Detection: UV (274 nm)
-Epoxy equivalent It measured by the method of JISK-7236.
Melting point: DSC method measuring machine; differential scanning calorimetry (DSC6200 Seiko Electronics Co., Ltd.)
Temperature rising rate: 10 ° C./min.
Bread; Al pan, melt viscosity measuring instrument in cone plate method at 150 ° C melt viscosity: Cone plate (ICI) high temperature viscometer (manufactured by RESEACH EQUIPMENT (LONDON) LTD.)
Corn No. : 3 (measurement range 0 to 2.00 Pa · s)
Sample amount: 0.15 ± 0.01 g
・ GPC
Column: GPC KF-803 + GPC KF-802.5 + GPC KF-802 + GPC KF-801
(Manufactured by Showa Denko)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1 ml / min.
Detection: RI
実施例１
攪拌機、温度計、コンデンサーを備えた四つ口フラスコにｐ−クレゾール７５７０部、ｐ−トルエンスルホン酸７部を仕込み、７０℃で攪拌しながら４，４’−ビス（クロロメチル）−１，１’−ビフェニル８７９部を２時間かけて加え、７０℃で２時間反応を行った。反応終了後、メチルイソブチルケトン１００００部を加え水洗を繰り返した。ついで油層から加熱減圧下、未反応ｐ−クレゾール及びメチルイソブチルケトンを留去することにより本発明のフェノール樹脂（Ｐ１）１２７３部を得た。得られたフェノール樹脂（Ｐ）の軟化点は５９℃、水酸基当量は２０３ｇ／ｅｑ、ＨＰＬＣ分析の結果、式（１）で表される化合物の含有量は７２面積％であった。
Example 1
A 4-necked flask equipped with a stirrer, a thermometer, and a condenser was charged with 7570 parts of p-cresol and 7 parts of p-toluenesulfonic acid, and stirred at 70 ° C., 4,4′-bis (chloromethyl) -1,1. 879 parts of '-biphenyl was added over 2 hours and reacted at 70 ° C for 2 hours. After completion of the reaction, 10,000 parts of methyl isobutyl ketone was added and washing with water was repeated. Next, 1273 parts of the phenol resin (P1) of the present invention was obtained by distilling off unreacted p-cresol and methyl isobutyl ketone from the oil layer under heating and reduced pressure. The softening point of the obtained phenol resin (P) was 59 ° C., the hydroxyl group equivalent was 203 g / eq, and as a result of HPLC analysis, the content of the compound represented by the formula (1) was 72 area%.
実施例２
攪拌機、温度計、コンデンサーを備えた四つ口フラスコに実施例１で得られたフェノール樹脂（Ｐ）８１３部、エピクロルヒドリン２２２１部、ジメチルスルホキシド５５５部を仕込み溶解後、５０℃に加熱し、フレーク状水酸化ナトリウム（純度９９％）１６５部を９０分かけて添加し、その後、さらに５０℃で２時間、７５℃で１時間反応させた。ついで反応混合物の水洗浄液が中性になるまで水洗を繰り返した後、油層から加熱減圧下、過剰のエピクロルヒドリンを留去し、残留物に２０７０部のメチルイソブチルケトンを添加し溶解した。さらにこのメチルイソブチルケトン溶液を７５℃に加熱し３０重量％の水酸化ナトリウム水溶液４０部を添加し、１時間反応させた後、反応混合物の水洗浄液が中性になるまで水洗を繰り返した。ついで油層から加熱減圧下、メチルイソブチルケトンを１８０℃にて留去、その後１３０℃にて攪拌、樹脂が結晶化により濁り始めたところで取り出すことによって本発明のエポキシ樹脂（Ｅ１）９９０部を得た。得られたエポキシ樹脂（Ｅ）は結晶性の固体であり、エポキシ当量は２７４ｇ／ｅｑ、軟化点は１３９℃、溶融粘度は０．０３Ｐａ・ｓであった。ＧＰＣ分析の結果、式（１）で表される化合物が主成分であるピーク面積は７３％であった。
Example 2
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 813 parts of the phenol resin (P) obtained in Example 1, 2221 parts of epichlorohydrin and 555 parts of dimethyl sulfoxide were charged and dissolved, and then heated to 50 ° C. to form a flake. 165 parts of sodium hydroxide (purity 99%) was added over 90 minutes, and then further reacted at 50 ° C. for 2 hours and at 75 ° C. for 1 hour. Subsequently, water washing was repeated until the water washing liquid of the reaction mixture became neutral, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 2070 parts of methyl isobutyl ketone was added to the residue and dissolved. Further, this methyl isobutyl ketone solution was heated to 75 ° C., 40 parts of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by repeated water washing until the water washing solution of the reaction mixture became neutral. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under reduced pressure by heating at 180 ° C., followed by stirring at 130 ° C., and taking out when the resin began to become turbid due to crystallization to obtain 990 parts of the epoxy resin (E1) of the present invention. . The obtained epoxy resin (E) was a crystalline solid, having an epoxy equivalent of 274 g / eq, a softening point of 139 ° C., and a melt viscosity of 0.03 Pa · s. As a result of GPC analysis, the peak area mainly composed of the compound represented by the formula (1) was 73%.
実施例３〜４、比較例１〜２
実施例２で得られたエポキシ樹脂（Ｅ）、比較用のエポキシ樹脂としてビフェニルノボラック型エポキシ樹脂（Ｒ）（ＮＣ−３０００：日本化薬（株）製）、硬化剤としてフェノールノボラック（軟化点８３℃、水酸基当量１０６ｇ／ｅｑ）、硬化促進剤としてトリフェニルホスフィン（純正化学（株）製）、無機充填剤として球状シリカ（ＭＳＲ−２２１２：龍森（株）製）を用いて表１の「配合物の組成の欄」に示す重量比で配合し、ロールで混練後、１７５℃、成型圧力７０Ｋｇ／ｃｍ２の条件でスパイラルフローを測定した（実施例３、比較例１）。また、無機充填剤を加えずに表１「配合物の組成の欄」に示す重量比で配合した組成物を１８０秒間トランスファー成型してその後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、ガラス転移温度（ＴＭＡ）、吸水率、アイゾッド衝撃試験の項目について以下の条件で試験を実施し表１の「硬化物の物性の欄」に示した（実施例４、比較例２）。
Examples 3-4, Comparative Examples 1-2
Epoxy resin (E) obtained in Example 2, biphenyl novolac type epoxy resin (R) (NC-3000: manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin for comparison, and phenol novolac (softening point 83) as a curing agent [Table 1], using triphenylphosphine (manufactured by Pure Chemical Co., Ltd.) as a curing accelerator and spherical silica (MSR-2212: manufactured by Tatsumori Co., Ltd.) as an inorganic filler. After blending at the weight ratio shown in the “Composition” column and kneading with a roll, spiral flow was measured under the conditions of 175 ° C. and a molding pressure of 70 kg / cm 2 (Example 3, Comparative Example 1). In addition, a composition blended at a weight ratio shown in Table 1 “Composition of composition” without adding an inorganic filler was transfer molded for 180 seconds and then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. A test piece was prepared and tested under the following conditions for the items of glass transition temperature (TMA), water absorption, and Izod impact test, and are shown in “Physical Properties of Cured Material” in Table 1 (Example 4, Comparative Example 2).
・ガラス転移温度
熱機械測定装置（ＴＭＡ）：真空理工 ＴＭ−７０００
昇温速度：２℃／ｍｉｎ．
・吸水率
試験片：直径５ｃｍ×厚み４ｍｍの円盤
１００℃の温水中で２４時間煮沸した後の重量増加量（重量％）
・アイゾッド衝撃試験
ＪＩＳ Ｋ−７７１０に準拠して測定
Glass transition temperature Thermomechanical measurement device (TMA): Vacuum Riko TM-7000
Temperature increase rate: 2 ° C./min.
-Water absorption rate Test piece: Disk of diameter 5 cm x thickness 4 mm Weight increase (% by weight) after boiling for 24 hours in warm water at 100 ° C
・ Izod impact test Measured according to JIS K-7710
表１
実施例３ 実施例４ 比較例１ 比較例２
配合物の組成
エポキシ樹脂（Ｅ） １２．３ １００
エポキシ樹脂（Ｒ） １２．３ １００
フェノールノボラック ４．６ ３８ ４．７ ３８
ＴＰＰ ０．２ １ ０．２ １
球状シリカ ８３．０ ８３．０
組成物の物性
スパイラルフロー（ｃｍ） ８５ ７１
硬化物の物性
ガラス転移点（℃） １３７ １４１
吸水率（％） ０．８ １．０
アイゾッド衝撃試験値
（ＫＪ／ｍ２） ３０ １７
Table 1
Example 3 Example 4 Comparative Example 1 Comparative Example 2
Composition of the compound Epoxy resin (E) 12.3 100
Epoxy resin (R) 12.3 100
Phenol novolac 4.6 38 4.7 38
TPP 0.2 1 0.2 1
Spherical silica 83.0 83.0
Physical properties of the composition Spiral flow (cm) 85 71
Physical properties of cured product Glass transition point (° C.) 137 141
Water absorption rate (%) 0.8 1.0
Izod impact test value (KJ / m 2 ) 30 17
このように本発明のエポキシ樹脂を用いたエポキシ樹脂組成物は、極めて低い粘度（フィラー含有量が８３％と比較的高いにも拘わらずスパイラルフローが長いことから判断される）を、また、その硬化物は優れた耐熱性、耐水性、耐衝撃性を示した。 Thus, the epoxy resin composition using the epoxy resin of the present invention has an extremely low viscosity (determined from a long spiral flow despite a relatively high filler content of 83%), and its The cured product showed excellent heat resistance, water resistance and impact resistance.
Claims (7)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190112365A (en) * | 2018-03-26 | 2019-10-07 | 동우 화인켐 주식회사 | Negative-type photosensitive resin comopsition |
| TWI877461B (en) * | 2021-03-18 | 2025-03-21 | 日商日本化藥股份有限公司 | Epoxy resin mixture and its manufacturing method, epoxy resin composition and its hardened product |
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| JPH05117350A (en) * | 1991-10-30 | 1993-05-14 | Nippon Steel Chem Co Ltd | Novel phenolic compound, epoxidized product thereof, and process for producing them |
| JP2002161129A (en) * | 2000-11-28 | 2002-06-04 | Nippon Kayaku Co Ltd | Polycresol resin, epoxy resin composition and cured product |
| JP2002322110A (en) * | 2001-04-27 | 2002-11-08 | Nippon Kayaku Co Ltd | New phenol compound |
| JP2002338656A (en) * | 2001-05-22 | 2002-11-27 | Nippon Kayaku Co Ltd | Crystalline epoxy resin, epoxy resin composition and cured product thereof |
| JP2005290319A (en) * | 2004-04-05 | 2005-10-20 | Ube Ind Ltd | Phenolic resin for rubber composition addition |
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2005
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05117350A (en) * | 1991-10-30 | 1993-05-14 | Nippon Steel Chem Co Ltd | Novel phenolic compound, epoxidized product thereof, and process for producing them |
| JP2002161129A (en) * | 2000-11-28 | 2002-06-04 | Nippon Kayaku Co Ltd | Polycresol resin, epoxy resin composition and cured product |
| JP2002322110A (en) * | 2001-04-27 | 2002-11-08 | Nippon Kayaku Co Ltd | New phenol compound |
| JP2002338656A (en) * | 2001-05-22 | 2002-11-27 | Nippon Kayaku Co Ltd | Crystalline epoxy resin, epoxy resin composition and cured product thereof |
| JP2005290319A (en) * | 2004-04-05 | 2005-10-20 | Ube Ind Ltd | Phenolic resin for rubber composition addition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190112365A (en) * | 2018-03-26 | 2019-10-07 | 동우 화인켐 주식회사 | Negative-type photosensitive resin comopsition |
| KR102383697B1 (en) | 2018-03-26 | 2022-04-05 | 동우 화인켐 주식회사 | Negative-type photosensitive resin comopsition |
| TWI877461B (en) * | 2021-03-18 | 2025-03-21 | 日商日本化藥股份有限公司 | Epoxy resin mixture and its manufacturing method, epoxy resin composition and its hardened product |
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