JP2010260802A - Dihydroxynaphthalene polymer, method of producing the same, and use therefor - Google Patents
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Abstract
Description
本発明は、成形材、各種バインダー、コーティング材、積層材などに有用なジヒドロキシナフタレン系重合体の製造方法、およびそれをエポキシ樹脂用硬化剤として用いた組成物、並びにその硬化物に関する。 The present invention relates to a method for producing a dihydroxynaphthalene polymer useful for molding materials, various binders, coating materials, laminated materials, and the like, a composition using the same as a curing agent for epoxy resins, and a cured product thereof.
半導体の封止材料としては、オルソクレゾールノボラック型エポキシ樹脂とフェノールノボラック樹脂を硬化剤に用い、シリカなどの充填材を配合した樹脂封止が適用されてきた。ＬＳＩチップの大型化、パッケージの薄型／小型化、実装方式の変更などに伴い、封止材への要求が大きく変わってきた。例えば、半田付け時の熱処理時に、吸湿水分の急激な気化膨張に伴うパッケージのクラックや、剥離が発生し問題になっている。このため、吸湿性が低く、半田付け温度における弾性率の低い、接着性に優れた硬化剤やエポキシ樹脂が望まれている。さらに近年は鉛フリー半田が使用されるようになり、求められる特性はますます厳しくなってきている。 As a semiconductor sealing material, resin sealing in which an ortho-cresol novolak type epoxy resin and a phenol novolak resin are used as a curing agent and a filler such as silica is blended has been applied. With the increase in size of LSI chips, thinness / miniaturization of packages, and changes in mounting methods, the demand for sealing materials has changed greatly. For example, during heat treatment at the time of soldering, cracks and peeling of the package due to rapid vaporization and expansion of moisture absorption moisture occur, which is a problem. For this reason, a curing agent or epoxy resin having low hygroscopicity, low elastic modulus at the soldering temperature and excellent adhesiveness is desired. In recent years, lead-free solder has been used, and the required characteristics have become increasingly severe.
一方で樹脂の難燃性に対する要求もますます高くなっているが、環境保全の観点から含臭素有機化合物や、アンチモン化合物などこれまで使用されてきた難燃剤の使用が制限され始めている。そのため難燃性に優れた硬化剤としてフェノールビフェニルアラルキル樹脂が使用されているが、ガラス転移温度（Ｔｇ）が低くなる欠点がある。 On the other hand, there is an increasing demand for flame retardancy of resins, but the use of flame retardants that have been used so far, such as bromine-containing organic compounds and antimony compounds, is beginning to be restricted from the viewpoint of environmental protection. Therefore, a phenol biphenyl aralkyl resin is used as a curing agent having excellent flame retardancy, but has a drawback that the glass transition temperature (Tg) is lowered.
フェノールビフェニルアラルキル樹脂は、難燃性に優れた硬化剤として使用されているが、それによって硬化されたエポキシ樹脂のガラス転移温度（Ｔｇ）が低くなる欠点がある。エポキシ樹脂のＴｇの低下は一般に高温信頼性と耐熱性の低下を引き起こすため、これを改善できるエポキシ樹脂硬化剤の提供が望まれていた。 The phenol biphenyl aralkyl resin is used as a curing agent having excellent flame retardancy, but has a drawback that the glass transition temperature (Tg) of the cured epoxy resin is lowered. Since a decrease in Tg of an epoxy resin generally causes a decrease in high temperature reliability and heat resistance, provision of an epoxy resin curing agent capable of improving this has been desired.
本発明者らは、このような課題を解決できる硬化剤について鋭意研究をした結果、特定のジヒドロキシナフタレン系重合物を使用することによって、課題を解決し得る硬化剤及び硬化物が得られることを見いだし、本発明に到達したものである。ナフタレン環含有重合物に関する公知文献としては、下記特許文献１があるが、同特許文献には一般式が記載されているもののナフタレン環含有重合物は具体的には記載されておらず、また同特許文献に記載の重合体では、上記課題を解決する硬化剤としては不十分であった。 As a result of intensive studies on a curing agent capable of solving such problems, the present inventors have found that a curing agent and a cured product that can solve the problem can be obtained by using a specific dihydroxynaphthalene-based polymer. As a result, the present invention has been achieved. As a publicly known document relating to a naphthalene ring-containing polymer, there is the following Patent Document 1, which does not specifically describe a naphthalene ring-containing polymer, although the general formula is described therein. The polymer described in the patent literature is insufficient as a curing agent that solves the above problems.
本発明者らは、上記従来技術の課題を解決できる硬化剤として、下記一般式（１）のジヒドロキシナフタレン系重合物を使用することによって、難燃性を維持しつつ従来品より硬化性が向上し、得られた樹脂のガラス転移温度（Ｔｇ）が高い硬化物が得られることを見いだし、本発明に到達した。 By using a dihydroxynaphthalene-based polymer represented by the following general formula (1) as a curing agent that can solve the above-described problems of the conventional technology, the inventors have improved curability compared to conventional products while maintaining flame retardancy. Then, it was found that a cured product having a high glass transition temperature (Tg) of the obtained resin was obtained, and the present invention was achieved.
本発明は、エポキシ樹脂硬化剤に適したジヒドロキシナフタレン系重合体を提供し、これからなる改善された硬化剤を提供するものである。 The present invention provides a dihydroxynaphthalene polymer suitable for an epoxy resin curing agent, and an improved curing agent comprising the same.
本発明は、このような硬化剤を含むエポキシ樹脂組成物およびその硬化物を提供するものである。 The present invention provides an epoxy resin composition containing such a curing agent and a cured product thereof.
本発明は、下記一般式（１）で表される重合体を提供する。 The present invention provides a polymer represented by the following general formula (1).
また本発明は、下記一般式（２）のジヒドロキシナフタレン類と、下記一般式（３）のビフェニル化合物と、下記一般式（４）の芳香族化合物を縮合反応させることを特徴とする前記一般式（１）のジヒドロキシナフタレン系重合体の製造方法を提供する。 The present invention is also characterized in that a dihydroxynaphthalene of the following general formula (2), a biphenyl compound of the following general formula (3), and an aromatic compound of the following general formula (4) are subjected to a condensation reaction. A method for producing the dihydroxynaphthalene polymer of (1) is provided.
本発明はまた、前記の一般式（１）のジヒドロキシナフタレン系重合体からなるエポキシ樹脂用硬化剤を提供する。 The present invention also provides a curing agent for an epoxy resin comprising the dihydroxynaphthalene polymer of the general formula (1).
本発明はさらに、前記の一般式（１）のジヒドロキシナフタレン系重合体とエポキシ樹脂とを含むエポキシ樹脂組成物およびそれを硬化させたエポキシ樹脂硬化物を提供する。 The present invention further provides an epoxy resin composition comprising the dihydroxynaphthalene polymer of the general formula (1) and an epoxy resin, and an epoxy resin cured product obtained by curing the epoxy resin composition.
本発明は、前記したエポキシ樹脂硬化物で封止された半導体装置も提供する。 The present invention also provides a semiconductor device sealed with the cured epoxy resin described above.
本発明により、速硬化性、低溶融粘度であって、高Ｔｇで、難燃性のエポキシ樹脂硬化物の提供が可能な硬化剤に適したジヒドロキシナフタレン系重合体が提供される。 According to the present invention, there is provided a dihydroxynaphthalene-based polymer suitable for a curing agent that can provide an epoxy resin cured product having a fast curing property, a low melt viscosity, a high Tg, and a flame retardancy.
本発明によって、速硬化性、低溶融粘度であって、高Ｔｇで、難燃性のエポキシ樹脂硬化物の提供が可能な硬化剤が提供される。 According to the present invention, there is provided a curing agent capable of providing an epoxy resin cured product having a fast curing property, a low melt viscosity, a high Tg, and a flame retardancy.
本発明により、本発明の硬化剤を含むエポキシ樹脂組成物およびその硬化物が提供される。 By this invention, the epoxy resin composition containing the hardening | curing agent of this invention and its hardened | cured material are provided.
本発明は、前期一般式（１）で示されるジヒドロキシナフタレン系重合体を提供するものである。 The present invention provides a dihydroxynaphthalene polymer represented by the general formula (1) in the previous period.
式（１）中、ｎは１〜１０であり、好ましくは１〜５である。また同式中、ｍは０〜４、式中ｍ´は０〜４であって、ｍ、ｍ´がそれぞれ、０〜３であることがより好ましい。但し、ｍ＋ｍ´は１以上である。 In formula (1), n is 1-10, Preferably it is 1-5. In the formula, m is 0 to 4, m ′ is 0 to 4, and m and m ′ are more preferably 0 to 3, respectively. However, m + m ′ is 1 or more.
前記一般式（１）で示されるジヒドロキシナフタレン系重合体の好ましい製造方法として、前期一般式（２）で示されるジヒドロキシナフタレン類と、前期一般式（３）で示されるビフェニル化合物と、前期一般式（４）で示される芳香族化合物類を、縮合反応させる製造方法を挙げることができる。 As a preferable production method of the dihydroxynaphthalene polymer represented by the general formula (1), the dihydroxynaphthalene represented by the general formula (2), the biphenyl compound represented by the general formula (3), and the general formula A production method in which the aromatic compound represented by (4) is subjected to a condensation reaction can be mentioned.
前記一般式（２）で示されるジヒドロキシナフタレン類と、前記一般式（３）で示されるビフェニル化合物と、前記一般式（４）で示される芳香族化合物との反応において、好ましくは、ジヒドロキシナフタレン類に対するビフェニル化合物のモル比が０．１〜０．６０、より好ましくは０．１５〜０．４０であり、ジヒドロキシナフタレン類に対する芳香族化合物のモル比が０．０５〜１．００、より好ましくは０．１０〜０．６０で反応させることが望ましい。 In the reaction of the dihydroxynaphthalene represented by the general formula (2), the biphenyl compound represented by the general formula (3), and the aromatic compound represented by the general formula (4), preferably dihydroxynaphthalenes The molar ratio of the biphenyl compound to 0.1 to 0.60, more preferably 0.15 to 0.40, and the molar ratio of the aromatic compound to the dihydroxynaphthalene is 0.05 to 1.00, more preferably It is desirable to react at 0.10 to 0.60.
さらに前記一般式（２）で示されるジヒドロキシナフタレン類として具体的には、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレンなどを挙げることができる。特に、１，６−ジヒドロキシナフタレンを使用するのが好ましい。 Specific examples of the dihydroxynaphthalene represented by the general formula (2) include 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7 -Dihydroxy naphthalene etc. can be mentioned. In particular, it is preferable to use 1,6-dihydroxynaphthalene.
一般式（３）で示されるビフェニル化合物として具体的には、４，４’−ビス（クロロメチル）ビフェニル、４，２’−ビス（クロロメチル）ビフェニル、２，２’−ビス（クロロメチル）ビフェニル、４，４’−ビス（メトキシメチル）ビフェニル、４，２’−ビス（メトキシメチル）ビフェニル、２，２’−ビス（メトキシメチル）ビフェニル、４，４’−ビス（ヒドロキシメチル）ビフェニル、４，２’−ビス（ヒドロキシメチル）ビフェニル、２，２’−ビス（ヒドロキシメチル）ビフェニルなどを挙げることができる。 Specific examples of the biphenyl compound represented by the general formula (3) include 4,4′-bis (chloromethyl) biphenyl, 4,2′-bis (chloromethyl) biphenyl, and 2,2′-bis (chloromethyl). Biphenyl, 4,4′-bis (methoxymethyl) biphenyl, 4,2′-bis (methoxymethyl) biphenyl, 2,2′-bis (methoxymethyl) biphenyl, 4,4′-bis (hydroxymethyl) biphenyl, 4,2′-bis (hydroxymethyl) biphenyl, 2,2′-bis (hydroxymethyl) biphenyl and the like can be mentioned.
一般式（４）で示される芳香族化合物としては、臭化ベンジル、塩化ベンジル、ベンジルアルコールなどを挙げることができる。特に、塩化ベンジルを使用するのが好ましい。 Examples of the aromatic compound represented by the general formula (4) include benzyl bromide, benzyl chloride, and benzyl alcohol. In particular, it is preferable to use benzyl chloride.
前記一般式（２）で示されるジヒドロキシナフタレン類と、前記一般式（３）で示されるビフェニル化合物と、前記一般式（４）で示される芳香族化合物類との縮合反応の反応条件としては、特に制限はなく、従来公知の縮合反応の条件から適宜選択して採用することができる。本発明の縮合反応は、酸触媒の存在下又は不存在下に、加熱処理することによって行うことができる。この反応において使用可能な酸触媒としては、リン酸、硫酸、塩酸などの無機酸、蓚酸、ベンゼンスルホン酸、トルエンスルホン酸、メタンスルホン酸、トリフロロメタンスルホン酸などの有機酸、塩化亜鉛、塩化第２錫、塩化第２鉄、ジエチル硫酸などのフリーデルクラフツ触媒を、単独で又は併用して用いることができる。 The reaction conditions for the condensation reaction of the dihydroxynaphthalene represented by the general formula (2), the biphenyl compound represented by the general formula (3) and the aromatic compound represented by the general formula (4) are as follows: There is no restriction | limiting in particular, It can select suitably from the conditions of a conventionally well-known condensation reaction, and can employ | adopt. The condensation reaction of the present invention can be carried out by heat treatment in the presence or absence of an acid catalyst. Acid catalysts that can be used in this reaction include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, zinc chloride, and chloride. Friedel-Crafts catalysts such as stannic chloride, ferric chloride, and diethyl sulfate can be used alone or in combination.
反応は、無溶媒でも、溶媒中でも行うことができる。用いることができる溶媒としては、ベンゼン、トルエン、メチルイソブチルケトン、１，４−ジオキサン、１−メトキシ−２−プロパノールなどを挙げることができる。 The reaction can be carried out without a solvent or in a solvent. Examples of the solvent that can be used include benzene, toluene, methyl isobutyl ketone, 1,4-dioxane, 1-methoxy-2-propanol, and the like.
反応は、８０〜２００℃程度の温度で、０．５〜１０時間程度維持することによって行うことができる。反応終了後、使用した溶媒は減圧下で除去することで前記一般式（１）で示される樹脂を得ることができる。 The reaction can be carried out by maintaining at a temperature of about 80 to 200 ° C. for about 0.5 to 10 hours. After completion of the reaction, the solvent used is removed under reduced pressure to obtain the resin represented by the general formula (1).
以下に実施例を用いて本発明をより詳細に説明する。本発明はこれらの例によって何ら制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples.
（実施例１）
１，６−ジヒドロキシナフタレン１２８．２ｇ（０．８０１モル）、４，４’−ビス（クロロメチル）ビフェニル４０．２ｇ（０．１６０モル）、１−メトキシ−２−プロパノール２５６．４ｇを、下部に抜出口のある４つ口フラスコに仕込み、撹拌させながら温度を上昇させ内温８０℃で触媒としてトリフロロメタンスルホン酸を５００ｐｐｍ。滴下する。その後、還流下において１２０℃まで昇温。１２０℃で４時間保持後、塩化ベンジル４６．５ｇ（０．３６９モル）を１時間かけて滴下し、さらに滴下後１時間保持した。反応で出てくるＨＣｌはそのまま系外へ揮散させ、アルカリ水でトラップした。この段階で未反応の４，４’−ビス（クロロメチル）ビフェニル及び塩化ベンジルは残存しておらず、全て反応したことをガスクロマトグラフィで確認後、ＤＢＵを５００ｐｐｍ添加し中和を行う。中和終了後、減圧することにより、系内に残存するＨＣｌ及び溶剤１−メトキシ−２−プロパノールを系外へ除去した。最終的に３０ｔｏｒｒで１５０℃まで減圧処理することで、残存溶剤がガスクロマトグラフィで未検出になった。この反応生成物を１５０℃に保持しながら、抜き出し、黒褐色なジヒドロキシナフタレン系重合体（１）１８８．５ｇを得た。
ジヒドロキシナフタレン系重合体（１）を、日本電子（株）製ＪＭＳ−７００高分解能質量検出器を用いてＦＤ−ＭＳ法により分子量測定を行って得られたチャートを図１に示す。
Example 1
128.2 g (0.801 mol) of 1,6-dihydroxynaphthalene, 40.2 g (0.160 mol) of 4,4′-bis (chloromethyl) biphenyl, 256.4 g of 1-methoxy-2-propanol, Into a four-necked flask with an outlet, the temperature was increased while stirring, and the internal temperature was 80 ° C., and 500 ppm of trifluoromethanesulfonic acid was used as a catalyst. Dripping. Thereafter, the temperature was raised to 120 ° C. under reflux. After maintaining at 120 ° C. for 4 hours, 46.5 g (0.369 mol) of benzyl chloride was added dropwise over 1 hour, and further maintained for 1 hour after the addition. HCl generated in the reaction was volatilized out of the system as it was and trapped with alkaline water. At this stage, unreacted 4,4′-bis (chloromethyl) biphenyl and benzyl chloride do not remain, and after confirming that all have reacted by gas chromatography, 500 ppm of DBU is added for neutralization. After completion of neutralization, the remaining pressure in the system and the solvent 1-methoxy-2-propanol were removed from the system by reducing the pressure. Finally, the remaining solvent was not detected by gas chromatography by reducing the pressure to 150 ° C. at 30 torr. The reaction product was withdrawn while maintaining at 150 ° C. to obtain 188.5 g of a dark brown dihydroxynaphthalene polymer (1).
FIG. 1 shows a chart obtained by measuring the molecular weight of the dihydroxynaphthalene polymer (1) by the FD-MS method using a JMS-700 high resolution mass detector manufactured by JEOL Ltd.
図１における質量ピークから、ジヒドロキシナフタレン系重合体（１）には、一般式（１）において、（ｍ′，ｍ，ｎ）＝（１，０，０）の重合体（分子量：２５０）、（ｍ′，ｍ，ｎ）＝（２，０，０）の重合体（分子量：３４０）、（ｍ′，ｍ，ｎ）＝（１，０，１又は０，１，１）の重合体（分子量：５８８）、（ｍ′，ｍ，ｎ）＝（２，０，１、又は１，１，１、又は０，２，１）の重合体（分子量：６７８）、（ｍ′，ｍ，ｎ）＝（３，０，１、又は２，１，１、又は１，２，１、又は０，３，１）の重合体（分子量：７６８）、（ｍ′，ｍ，ｎ）＝（１，０，２）の重合体（分子量：９２６）、（ｍ′，ｍ，ｎ）＝（２，０，２、又は０，１，２）の重合体（分子量：１０１６）に該当する各種重合体が含まれていることが判った。 From the mass peak in FIG. 1, the dihydroxynaphthalene polymer (1) is a polymer (molecular weight: 250) of (m ′, m, n) = (1, 0, 0) in the general formula (1), (M ′, m, n) = (2,0,0) polymer (molecular weight: 340), (m ′, m, n) = (1,0,1 or 0,1,1) polymer (Molecular weight: 588), (m ′, m, n) = (2,0,1, or 1,1,1, or 0,2,1) polymer (molecular weight: 678), (m ′, m , N) = (3,0,1, or 2,1,1 or 1,2,1, or 0,3,1) polymer (molecular weight: 768), (m ′, m, n) = (1,0,2) polymer (molecular weight: 926), (m ', m, n) = (2, 0, 2, or 0, 1, 2) polymer (molecular weight: 1016) It turns out that various polymers are included. .
このジヒドロキシナフタレン系重合体（１）のＪＩＳ Ｋ ２２０７に基づく軟化点は７９℃であった。またＩＣＩ溶融粘度計により測定した１５０℃における溶融粘度は１８０ｍＰａ・ｓであった。さらにアセチル化逆滴定法により測定した水酸基当量は１１８ｇ／ｅｑであった。 The softening point of this dihydroxynaphthalene polymer (1) based on JIS K 2207 was 79 ° C. The melt viscosity at 150 ° C. measured by an ICI melt viscometer was 180 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 118 g / eq.
（実施例２）
１，６−ジヒドロキシナフタレンの仕込み量を１３９．７ｇ（０．８７３モル）、４，４’−ビス（クロロメチル）ビフェニルの仕込み量を４３．８ｇ（０．１７５モル）、１−メトキシ−２−プロパノール２７９．４ｇ、塩化ベンジルの仕込み量を２２．０ｇ（０．１７５モル）とした以外は、実施例１と同様にして行い、黒褐色のジヒドロキシナフタレン系重合体（２）１８２．０ｇを得た。
(Example 2)
The amount of 1,6-dihydroxynaphthalene charged was 139.7 g (0.873 mol), the amount of 4,4′-bis (chloromethyl) biphenyl charged was 43.8 g (0.175 mol), and 1-methoxy-2 The same procedure as in Example 1 was carried out except that 279.4 g of propanol and the amount of benzyl chloride charged were 22.0 g (0.175 mol) to obtain 182.0 g of a blackish brown dihydroxynaphthalene polymer (2). It was.
このジヒドロキシナフタレン系重合体（２）のＪＩＳ Ｋ ２２０７に基づく軟化点は７３℃であった。またＩＣＩ溶融粘度計により測定した１５０℃における溶融粘度は１２０ｍＰａ・ｓであった。さらにアセチル化逆滴定法により測定した水酸基当量は１０７ｇ／ｅｑであった。 The softening point of this dihydroxynaphthalene polymer (2) based on JIS K 2207 was 73 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 120 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 107 g / eq.
（実施例３）
１，６−ジヒドロキシナフタレンの仕込み量を１２７．０ｇ（０．７９４モル）、４，４’−ビス（クロロメチル）ビフェニルの仕込み量を４９．０ｇ（０．１９８モル）、１−メトキシ−２−プロパノール２５４．０ｇ、塩化ベンジルの仕込み量を２０．０ｇ（０．１５９モル）とした以外は、実施例１と同様にして行い、黒褐色のジヒドロキシナフタレン系重合体（４）１４８．９ｇを得た。
(Example 3)
The amount of 1,6-dihydroxynaphthalene charged was 127.0 g (0.794 mol), the amount of 4,4′-bis (chloromethyl) biphenyl charged was 49.0 g (0.198 mol), and 1-methoxy-2 Except for 254.0 g of propanol and 20.0 g (0.159 mol) of benzyl chloride, the same procedure as in Example 1 was carried out to obtain 148.9 g of a blackish brown dihydroxynaphthalene polymer (4). It was.
このジヒドロキシナフタレン系重合体（３）のＪＩＳ Ｋ ２２０７に基づく軟化点は８４℃であった。またＩＣＩ溶融粘度計により測定した１５０℃における溶融粘度は３１０ｍＰａ・ｓであった。さらにアセチル化逆滴定法により測定した水酸基当量は１０９ｇ／ｅｑであった。 The softening point of this dihydroxynaphthalene polymer (3) based on JIS K 2207 was 84 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 310 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 109 g / eq.
（実施例４）
１，６−ジヒドロキシナフタレン／２，７−ジヒドロキシナフタレンの仕込み比率を７／３で仕込み量を１３９．７ｇ（０．８７３モル）、４，４’−ビス（クロロメチル）ビフェニルの仕込み量を４３．８ｇ（０．１７５モル）、１−メトキシ−２−プロパノール２７９．４ｇ、塩化ベンジルの仕込み量を２２．０ｇ（０．１７５モル）とした以外は、実施例１と同様にして行い、黒褐色のジヒドロキシナフタレン系重合体（４）１８２．５ｇを得た。
Example 4
The charging ratio of 1,6-dihydroxynaphthalene / 2,7-dihydroxynaphthalene was 7/3, the charging amount was 139.7 g (0.873 mol), and the charging amount of 4,4′-bis (chloromethyl) biphenyl was 43. 0.8 g (0.175 mol), 1-methoxy-2-propanol 279.4 g, and the amount of benzyl chloride charged was changed to 22.0 g (0.175 mol). 182.5 g of a dihydroxynaphthalene polymer (4) was obtained.
このジヒドロキシナフタレン系重合体（４）のＪＩＳ Ｋ ２２０７に基づく軟化点は９０℃であった。またＩＣＩ溶融粘度計により測定した１５０℃における溶融粘度は７００ｍＰａ・ｓであった。さらにアセチル化逆滴定法により測定した水酸基当量は１０６ｇ／ｅｑであった。 The softening point of this dihydroxynaphthalene polymer (4) based on JIS K 2207 was 90 ° C. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 700 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 106 g / eq.
実施例１〜４で得られたジヒドロキシナフタレン系重合体(１)〜(４)の物性を、後記比較例１で使用したフェノールアラルキル樹脂と対比して表１に示した。 The physical properties of the dihydroxynaphthalene polymers (1) to (4) obtained in Examples 1 to 4 are shown in Table 1 in comparison with the phenol aralkyl resin used in Comparative Example 1 described later.
（実施例５）
下記一般式（５）
で示されるエポキシ樹脂Ａ（ビフェニルアラルキル型、エポキシ当量２７２ｇ／ｅｑ、日本化薬（株）製ＮＣ−３０００Ｐ）、実施例１で得たジヒドロキシナフタレン系重合体（１）、溶融シリカ及びリン系硬化促進剤（２−（トリフェニルホスホニオ）フェノラート）を表２に示す割合で配合し、充分に混合した後、８５℃±３℃の２本ロールで３分混練し、冷却、粉砕することにより、成形用組成物を得た。トランスファー成形機でこの成形用組成物を、圧力１００ｋｇｆ／ｃｍ２で１７５℃、２分間成形した後、１８０℃、６時間のポストキュアを行い、ガラス転移温度（Ｔｇ）用及び難燃性試験用のテストピースを得た。
(Example 5)
The following general formula (5)
Epoxy resin A (biphenyl aralkyl type, epoxy equivalent 272 g / eq, NC-3000P manufactured by Nippon Kayaku Co., Ltd.), dihydroxynaphthalene polymer (1) obtained in Example 1, fused silica and phosphorus-based curing By blending the accelerator (2- (triphenylphosphonio) phenolate) in the proportions shown in Table 2 and mixing thoroughly, the mixture is kneaded with two rolls at 85 ° C. ± 3 ° C. for 3 minutes, cooled and ground. A molding composition was obtained. This molding composition was molded with a transfer molding machine at a pressure of 100 kgf / cm 2 at 175 ° C. for 2 minutes, and then post-cured at 180 ° C. for 6 hours for glass transition temperature (Tg) and flame resistance test. I got a test piece.
これら成形材料の物性を、次の方法により測定した。
（１）ガラス転移温度（Ｔｇ）
ＴＭＡにより、昇温速度１０℃／分の条件で線膨張係数を測定し、線膨張係数の変曲点をＴｇとした。
（２）難燃性
厚み１．６ｍｍ×幅１０ｍｍ×長さ１３５ｍｍのサンプルを用い、ＵＬ−Ｖ９４に準拠して残炎時間を測定し、難燃性を評価した。これらの評価結果を表２に示す。
The physical properties of these molding materials were measured by the following method.
(1) Glass transition temperature (Tg)
The linear expansion coefficient was measured by TMA at a temperature increase rate of 10 ° C./min, and the inflection point of the linear expansion coefficient was defined as Tg.
(2) Flame retardancy Using a sample having a thickness of 1.6 mm × width 10 mm × length 135 mm, the afterflame time was measured according to UL-V94, and the flame retardancy was evaluated. These evaluation results are shown in Table 2.
（３）硬化性
キュラストメーター（オリエンテック（株）製、ＪＳＲキュラストメーターＶＰＳ型）を用い、試料５ｇを金型温度１７５℃、加熱開始６０秒後、９０秒後、３００秒後のトルクを求めた。
(3) Curability Using a curast meter (Orientec Co., Ltd., JSR curast meter VPS type), a sample 5g was subjected to a mold temperature of 175 ° C., 60 seconds after starting heating, 90 seconds later, and 300 seconds after torque Asked.
（実施例６）
実施例１で得たジヒドロキシナフタレン系重合体(１)の代わりに、実施例２で得たジヒドロキシナフタレン系重合体（２）を用い、配合割合を表１のようにした以外は、実施例５と同様にして成形用組成物を調製し、その評価を行った。その結果を表２に示す。
(Example 6)
Example 5 except that the dihydroxynaphthalene polymer (2) obtained in Example 2 was used in place of the dihydroxynaphthalene polymer (1) obtained in Example 1, and the blending ratio was as shown in Table 1. In the same manner as above, a molding composition was prepared and evaluated. The results are shown in Table 2.
（実施例７）
実施例１で得たジヒドロキシナフタレン系重合体(１)の代わりに、実施例３で得たジヒドロキシナフタレン系重合体(３)を用い、配合割合を表１のようにした以外は、実施例５と同様にして成形用組成物を調製し、その評価を行った。その結果を表２に示す。
(Example 7)
Example 5 except that the dihydroxynaphthalene polymer (3) obtained in Example 3 was used in place of the dihydroxynaphthalene polymer (1) obtained in Example 1 and the blending ratio was as shown in Table 1. In the same manner as above, a molding composition was prepared and evaluated. The results are shown in Table 2.
（実施例８）
実施例１で得たジヒドロキシナフタレン系重合体(１)の代わりに、実施例４で得たジヒドロキシナフタレン系重合体(４)を用い、配合割合を表１のようにした以外は、実施例５と同様にして成形用組成物を調製し、その評価を行った。その結果を表２に示す。
(Example 8)
Example 5 except that the dihydroxynaphthalene polymer (4) obtained in Example 4 was used in place of the dihydroxynaphthalene polymer (1) obtained in Example 1, and the blending ratio was as shown in Table 1. In the same manner as above, a molding composition was prepared and evaluated. The results are shown in Table 2.
（比較例１）
実施例１で得たジヒドロキシナフタレン系重合体(１)の代わりに、下記一般式（６）で示されるフェノールアラルキル樹脂（ＩＣＩ溶融粘度計により測定した１５０℃における溶融粘度は２００ｍＰａ・ｓ、水酸基当量１７５ｇ／ｅｑ）を用いると共に、配合割合を表１のようにした以外は、実施例４と同様にして成形用組成物を調製し、その評価を行った。その結果を表２に示す。
(Comparative Example 1)
Instead of the dihydroxynaphthalene polymer (1) obtained in Example 1, a phenol aralkyl resin represented by the following general formula (6) (melt viscosity at 150 ° C. measured by an ICI melt viscometer is 200 mPa · s, hydroxyl equivalent) 175 g / eq) was used, and a molding composition was prepared and evaluated in the same manner as in Example 4 except that the blending ratio was as shown in Table 1. The results are shown in Table 2.
表２より、実施例５〜８の樹脂組成物は、比較例１より硬化性が優れ、高いガラス転移温度を示し、難燃性評価についても比較例１と同等であった。 From Table 2, the resin composition of Examples 5-8 was excellent in sclerosis | hardenability compared with the comparative example 1, the high glass transition temperature was shown, and the flame retardance evaluation was also equivalent to the comparative example 1.
本発明により、速硬化性、低溶融粘度であって、高Ｔｇで、難燃性のエポキシ樹脂硬化物の提供が可能な硬化剤に適した前記一般式（１）のジヒドロキシナフタレン系重合体が提供される。
本発明によって、速硬化性、低溶融粘度であって、高Ｔｇで、難燃性のエポキシ樹脂硬化物の提供が可能な硬化剤が提供される。
本発明により、本発明の硬化剤を含むエポキシ樹脂組成物およびその硬化物が提供される。
前記一般式（１）のジヒドロキシナフタレン系重合物を硬化剤として使用することによって、従来品より硬化性が向上し、得られた樹脂のガラス転移温度（Ｔｇ）が高いエポキシ樹脂組成物およびその硬化物が提供される。
According to the present invention, there is provided a dihydroxynaphthalene-based polymer of the above general formula (1) suitable for a curing agent capable of providing a hardened epoxy resin cured product having a fast curing property, a low melt viscosity and a high Tg. Provided.
According to the present invention, there is provided a curing agent capable of providing an epoxy resin cured product having a fast curing property, a low melt viscosity, a high Tg, and a flame retardancy.
By this invention, the epoxy resin composition containing the hardening | curing agent of this invention and its hardened | cured material are provided.
By using the dihydroxynaphthalene polymer of the general formula (1) as a curing agent, the curability is improved as compared with the conventional product, and the resulting resin has a high glass transition temperature (Tg) and its curing. Things are provided.
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| JP5166610B2 (en) * | 2009-12-14 | 2013-03-21 | 新日鉄住金化学株式会社 | Epoxy resin, production method thereof, epoxy resin composition and cured product using the same |
| WO2015146606A1 (en) * | 2014-03-28 | 2015-10-01 | 新日鉄住金化学株式会社 | Epoxy resin, epoxy resin composition, and cured product of same |
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| JPH04304225A (en) * | 1991-04-01 | 1992-10-27 | Nippon Kayaku Co Ltd | New compound, resin, resin composition, and cured article |
| JPH06271654A (en) * | 1993-03-22 | 1994-09-27 | Nippon Kayaku Co Ltd | Naphthalene ring-containing resin, resin composition and its cured product |
| JPH11255688A (en) * | 1998-03-10 | 1999-09-21 | Nippon Steel Chem Co Ltd | New polyhydric hydroxy compound, new epoxy compound, their production, epoxy resin composition and cured product using the same |
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| JPH0474146A (en) * | 1990-07-16 | 1992-03-09 | Nippon Steel Chem Co Ltd | New polyhydric hydroxyl compound and production thereof |
| JPH04304225A (en) * | 1991-04-01 | 1992-10-27 | Nippon Kayaku Co Ltd | New compound, resin, resin composition, and cured article |
| JPH06271654A (en) * | 1993-03-22 | 1994-09-27 | Nippon Kayaku Co Ltd | Naphthalene ring-containing resin, resin composition and its cured product |
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| JP5166610B2 (en) * | 2009-12-14 | 2013-03-21 | 新日鉄住金化学株式会社 | Epoxy resin, production method thereof, epoxy resin composition and cured product using the same |
| WO2015146606A1 (en) * | 2014-03-28 | 2015-10-01 | 新日鉄住金化学株式会社 | Epoxy resin, epoxy resin composition, and cured product of same |
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