JP2012171971A - Thermosetting resin composition and cured product thereof - Google Patents
Thermosetting resin composition and cured product thereof Download PDFInfo
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本発明は、難燃性、機械的強度、耐熱性など、硬化速度に優れ、電子・電気機器用の材料として有用な熱硬化性樹脂組成物およびその硬化物に関する。 The present invention relates to a thermosetting resin composition that is excellent in curing speed, such as flame retardancy, mechanical strength, and heat resistance, and is useful as a material for electronic and electrical equipment, and a cured product thereof.
ベンゾオキサジンは、ジヒドロ−１,３−ベンゾオキサジン環を有する化合物をいい、加熱すると耐熱性、難燃性に優れた硬化物となることが知られている（特許文献１参照）。ベンゾオキサジンは、適当な加熱により開環してフェノール性構造を形成することからフェノール樹脂に大別されることも多いが、開環に基づく硬化では揮発性の副生成物を発生しない。このため、特に、現在フェノール樹脂が用いられている電子・電気機器分野において、成形加工時に副生ガスを発生しない新しい熱硬化性樹脂材料として注目されている。また、難燃性に優れることから、建築材料、航空機、自動車などの構造材料としても有用である。 Benzoxazine refers to a compound having a dihydro-1,3-benzoxazine ring, and is known to be a cured product having excellent heat resistance and flame retardancy when heated (see Patent Document 1). Benzoxazine ring-opens by appropriate heating to form a phenolic structure, and is therefore broadly classified as a phenol resin. However, curing based on ring-opening does not generate volatile by-products. For this reason, in particular, in the electronic / electric equipment field where phenolic resins are currently used, it has been attracting attention as a new thermosetting resin material that does not generate by-product gas during molding. Moreover, since it is excellent in flame retardancy, it is also useful as a structural material for building materials, aircraft, automobiles and the like.
しかしながら、ベンゾオキサジンの硬化速度は、一般的なノボラックもしくはレゾール型のフェノール樹脂あるいはエポキシ樹脂などの熱硬化性樹脂に比べ、必ずしも満足のいくものではない。これに対し、ベンゾオキサジンに、芳香族スルホン酸含有シクロヘキシル誘導体を硬化触媒として添加して、硬化速度を上げる試みがなされている（特許文献２〜３参照）。 However, the curing rate of benzoxazine is not always satisfactory as compared with general novolak or resol type phenolic resins or epoxy resins. In contrast, attempts have been made to increase the curing rate by adding an aromatic sulfonic acid-containing cyclohexyl derivative to benzoxazine as a curing catalyst (see Patent Documents 2 and 3).
本発明は、ベンゾオキサジンの硬化速度を改善することを課題とする。 An object of the present invention is to improve the curing rate of benzoxazine.
本発明では、ベンゾオキサジンにジシクロペンタジエン変性フェノールを加えることで硬化速度を改善された熱硬化性樹脂組成物を得ている。
このような本発明の第１の態様として、
ベンゾオキサジン：５０〜９９質量％、およびジシクロペンタジエン変性フェノール：５０〜１質量％を含有する熱硬化性樹脂組成物を提供する。
In the present invention, a thermosetting resin composition having an improved curing rate is obtained by adding dicyclopentadiene-modified phenol to benzoxazine.
As such a first aspect of the present invention,
Provided is a thermosetting resin composition containing 50 to 99% by mass of benzoxazine and 50 to 1% by mass of dicyclopentadiene-modified phenol.
本発明の別の態様として、さらにノボラック樹脂を、熱硬化性樹脂組成物全量１００質量％に対し０.１〜３０質量％含有する熱硬化性樹脂組成物を提供する。 As another aspect of the present invention, there is further provided a thermosetting resin composition containing 0.1 to 30% by mass of a novolak resin with respect to 100% by mass of the total amount of the thermosetting resin composition.
さらなる態様として、さらに、シリカを、熱硬化性樹脂組成物全量１００質量％に対し１〜９０質量％含有する熱硬化性樹脂組成物を提供する。 As a further aspect, there is further provided a thermosetting resin composition containing 1 to 90% by mass of silica with respect to 100% by mass of the total amount of the thermosetting resin composition.
本発明では、上記のような熱硬化性樹脂組成物が熱硬化してなる樹脂硬化物も提供する。 The present invention also provides a cured resin product obtained by thermosetting the thermosetting resin composition as described above.
上記のような本発明の熱硬化性樹脂組成物は、ベンゾオキサジンに比べて硬化速度が著しく速い。このような本発明の組成物により、従来、硬化速度が遅く、生産性に問題のあったベンゾオキサジン硬化物を高い生産性で製造することが可能となる。また、硬化剤として前記シクロヘキシル誘導体を用いる場合のようなコスト高の問題を避けることができる。本発明の組成物を硬化させた硬化物は、耐熱性、難燃性に優れるため、半導体封止剤やプリント配線基板積層板、成形材料などとして有用である。 The thermosetting resin composition of the present invention as described above has a markedly faster curing rate than benzoxazine. Such a composition of the present invention makes it possible to produce a benzoxazine cured product having a low curing rate and a problem in productivity with high productivity. Moreover, the problem of high cost like the case where the said cyclohexyl derivative is used as a hardening | curing agent can be avoided. Since the cured product obtained by curing the composition of the present invention is excellent in heat resistance and flame retardancy, it is useful as a semiconductor encapsulant, a printed wiring board laminate, a molding material, and the like.
以下、本発明をより具体的に説明する。
ベンゾオキサジンは、ジヒドロ−１,３−ベンゾオキサジン環（以下、単に「オキサジン環」と表記することもある）を有する化合物である。
ベンゾオキサジンは、アミン類、フェノール類、ホルムアルデヒド類の縮合物であり、通常、これら反応原料のフェノール類、アミン類の置換基、種類などによって生成するベンゾオキサジンの化学構造が決まる。下記に基本的な合成スキームを示す。
Benzoxazine is a compound having a dihydro-1,3-benzoxazine ring (hereinafter sometimes simply referred to as “oxazine ring”).
Benzoxazine is a condensate of amines, phenols, and formaldehydes, and the chemical structure of benzoxazine produced is usually determined by the phenols, amine substituents, and types of these reaction raw materials. The basic synthesis scheme is shown below.
本発明で用いられるベンゾオキサジンは、「オキサジン環」の誘導体であればよく、特に制限されないが、１分子中に少なくとも２つのオキサジン環を有する化合物が好ましく挙げられる。これは、架橋密度が高くなり、耐熱性の向上などの面で優れるからである。 The benzoxazine used in the present invention is not particularly limited as long as it is a derivative of an “oxazine ring”, but a compound having at least two oxazine rings in one molecule is preferably exemplified. This is because the crosslink density is increased and the heat resistance is improved.
オキサジン環を少なくとも２つ有するベンゾオキサジンを誘導するためのアミン類としては、ジアミンを用いることができる。ジアミンとしては、例えば、４，４’−オキシジアニリン、４，４’−ジアミノジフェニルメタン、パラジアミノベンゼン、およびこれらにアルキル基、アルコキシ基、ハロゲン、芳香族炭化水素基などが置換された化合物などが挙げられる。これらの中でも、耐熱性や難燃性に優れたベンゾオキサジンが得られる点から、４，４’−オキシジアニリンが好ましい。
また、アニリン、アニリンにアルキル基、アルコキシ基、ハロゲンなどが置換されたものなどの１級アミンも用いられる。これらのうちでは、アニリンが安価で好ましい。
As the amines for deriving benzoxazine having at least two oxazine rings, diamines can be used. Examples of the diamine include 4,4′-oxydianiline, 4,4′-diaminodiphenylmethane, paradiaminobenzene, and compounds in which an alkyl group, an alkoxy group, a halogen, an aromatic hydrocarbon group, or the like is substituted. Is mentioned. Among these, 4,4′-oxydianiline is preferable because benzoxazine excellent in heat resistance and flame retardancy can be obtained.
In addition, primary amines such as aniline or aniline substituted with an alkyl group, an alkoxy group, halogen, or the like are also used. Of these, aniline is inexpensive and preferred.
また、フェノール類は、１価でも多価でもよい。１価フェノール類としては、フェノール、クレゾール、キシレノール、ナフトールなどが挙げられ、多価フェノール類としては、ビスフェールなどが挙げられる。これらにアルキル基、アルコキシ基、ハロゲン、芳香族炭化水素基などが置換された化合物も挙げられる。
ビスフェールは、具体的にビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、などが挙げられる。
これらの中では、安価なフェノール、クレゾール、ビスフェノールＡが好ましい。
The phenols may be monovalent or polyvalent. Examples of monohydric phenols include phenol, cresol, xylenol, and naphthol. Examples of polyhydric phenols include bisphenol. These include compounds in which an alkyl group, an alkoxy group, a halogen, an aromatic hydrocarbon group, or the like is substituted.
Specific examples of the bisfer include bisphenol A, bisphenol F, and bisphenol S.
In these, cheap phenol, cresol, and bisphenol A are preferable.
ホルムアルデヒド類は、ホルムアルデヒド（水溶液）、パラホルムアルデヒドなどが用いられる。上記のようなアミン類、フェノール類、ホルムアルデヒド類からベンゾオキサジンを得るには、公知の方法を広く採用することができる。
オキサジン環を少なくとも２つ有するベンゾオキサジンは、ジアミン類、フェノール類およびホルムアルデヒド類を反応させる方法、ビスフェノール類、１級アミンおよびホルムアルデヒド類を反応させる方法などにより製造することができる。
As the formaldehyde, formaldehyde (aqueous solution), paraformaldehyde and the like are used. In order to obtain benzoxazine from amines, phenols, and formaldehydes as described above, known methods can be widely employed.
Benzoxazine having at least two oxazine rings can be produced by a method of reacting diamines, phenols and formaldehyde, a method of reacting bisphenols, primary amines and formaldehyde.
本発明で用いられるジシクロペンタジエン変性フェノールは、フェノール類とジシクロペンタジエン類を酸触媒とともに加熱することにより製造することができる。
ジシクロペンタジエン変性フェノールの製造に用いられるフェノール類は、特に限定されないが、好ましくは、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、２，６−キシレノール、およびこれらの混合物を挙げることができる。中でも、樹脂の特性や経済性の点から、フェノールが最も好ましい。また、本発明で用いられるジシクロペンタジエン類も特に限定されないが、好ましくは、ジシクロペンタジエンや、ジシクロペンタジエンに、少なくとも１個のアルキル基またはビニル基が置換された化合物、およびこれらの混合物を挙げることができる。中でも、樹脂の特性や入手の容易さから、ジシクロペンタジエンが最も好ましい。
The dicyclopentadiene-modified phenol used in the present invention can be produced by heating phenols and dicyclopentadiene together with an acid catalyst.
The phenols used for the production of dicyclopentadiene-modified phenol are not particularly limited, but preferably include phenol, o-cresol, m-cresol, p-cresol, 2,6-xylenol, and mixtures thereof. it can. Of these, phenol is most preferable from the viewpoint of the characteristics and economical efficiency of the resin. The dicyclopentadiene used in the present invention is not particularly limited. Preferably, dicyclopentadiene, a compound in which at least one alkyl group or vinyl group is substituted on dicyclopentadiene, and a mixture thereof are used. Can be mentioned. Among these, dicyclopentadiene is most preferable because of the characteristics of the resin and availability.
酸触媒としては、三フッ化ホウ素、三フッ化ホウ素フェノール錯体、三フッ化ホウ素エーテル錯体などが反応性が高く好ましい。
ジシクロペンタジエン変性フェノールの製造では、触媒は、反応が終了した後、アルカリ性の触媒中和剤を用いて中和される。これは、反応終了後に触媒が残存していると、後工程の未反応フェノールを蒸留除去する段階で反応が過度に進行する可能性があるからである。触媒を中和した後は、中和剤や触媒残渣を除去するために、濾過を行なう。濾過により、中和剤や触媒残渣からなる固形分と、未反応フェノールや反応生成物からなるろ液に分別される。最後にろ液を減圧蒸留して、未反応フェノールを蒸留除去し、ジシクロペンタジエン変性フェノール樹脂を回収する。
As the acid catalyst, boron trifluoride, boron trifluoride phenol complex, boron trifluoride ether complex and the like are preferable because of high reactivity.
In the production of dicyclopentadiene-modified phenol, the catalyst is neutralized with an alkaline catalyst neutralizer after the reaction is complete. This is because if the catalyst remains after completion of the reaction, the reaction may proceed excessively at the stage where the unreacted phenol in the subsequent step is removed by distillation. After neutralizing the catalyst, filtration is performed to remove the neutralizing agent and catalyst residues. By filtration, it is separated into a solid content composed of a neutralizing agent and a catalyst residue and a filtrate composed of unreacted phenol and reaction products. Finally, the filtrate is distilled under reduced pressure to distill off unreacted phenol, and the dicyclopentadiene-modified phenol resin is recovered.
フェノール類とジシクロペンタジエン類を反応させる場合は、その仕込比を調節する事で得られるフェノール樹脂の軟化点を調節することができる。すなわち、フェノールの仕込割合を増やすと軟化点は低下し、フェノールの仕込割合を減らすと軟化点は向上する。フェノール類とジシクロペンタジエン類の仕込比として好適な範囲は、フェノール／ジシクロペンタジエン＝１／１〜１５／１（モル比）である。これよりもフェノールの割合が少ない場合や多い場合は、工業的に有用な軟化点を有するジシクロペンタジエン変性フェノール樹脂を得ることができない。
フェノール類とジシクロペンタジエン類を反応させる際に用いられる触媒は、三フッ化ホウ素、三フッ化ホウ素フェノール錯体、三フッ化ホウ素エーテル錯体などが好適である。これらの中でも、取扱いが容易で、反応性が高い三フッ化ホウ素フェノール錯体が好ましい。
When the phenols and dicyclopentadiene are reacted, the softening point of the phenol resin obtained can be adjusted by adjusting the charging ratio. That is, the softening point decreases when the phenol charge ratio is increased, and the softening point increases when the phenol charge ratio is decreased. A suitable range for the charge ratio of phenols and dicyclopentadiene is phenol / dicyclopentadiene = 1/1 to 15/1 (molar ratio). When the proportion of phenol is smaller or larger than this, an industrially useful dicyclopentadiene-modified phenol resin having a softening point cannot be obtained.
The catalyst used when the phenols and dicyclopentadiene are reacted is preferably boron trifluoride, boron trifluoride phenol complex, boron trifluoride ether complex or the like. Among these, a boron trifluoride phenol complex that is easy to handle and highly reactive is preferable.
本発明に係る熱硬化性樹脂組成物は、上記のようなベンゾオキサジン５０〜９９質量％、ジシクロペンタジエン変性フェノール１〜５０質量％を含む。ジシクロペンタジエン変性フェノールの量が１質量％よりも少ないと硬化速度が改善効果が得られず、一方、５０質量％よりも多いと耐熱性などが低下する傾向がある。本発明に係る熱硬化性樹脂組成物は、好ましくはベンゾオキサジン７０〜９７質量％、ジシクロペンタジエン変性フェノール３〜３０質量％を含む。 The thermosetting resin composition according to the present invention contains 50 to 99% by mass of benzoxazine as described above and 1 to 50% by mass of dicyclopentadiene-modified phenol. If the amount of the dicyclopentadiene-modified phenol is less than 1% by mass, the effect of improving the curing rate cannot be obtained. On the other hand, if it exceeds 50% by mass, the heat resistance tends to decrease. The thermosetting resin composition according to the present invention preferably contains 70 to 97% by mass of benzoxazine and 3 to 30% by mass of dicyclopentadiene-modified phenol.
これらの樹脂組成物を製造する方法は、特に限定されないが、所定量のベンゾオキサジンとジシクロペンタジエン変性フェノールを１００℃〜２５０℃、好ましくは、１２０℃〜２００℃、更に好ましくは、１３０℃〜１８０℃の範囲に加熱して溶融させ、各種ミキサーや押出機を用いて混練する方法、所定量のベンゾオキサジンとジシクロペンタジエン変性フェノールをトルエンやメチルエチルケトン、アセトンなどの溶媒に溶かして、溶液状態にし、両者を混合した後、溶媒を蒸留除去する方法などが挙げられる。 The method for producing these resin compositions is not particularly limited, but a predetermined amount of benzoxazine and dicyclopentadiene-modified phenol is 100 ° C to 250 ° C, preferably 120 ° C to 200 ° C, more preferably 130 ° C to A method of heating and melting in the range of 180 ° C., kneading using various mixers and extruders, dissolving a predetermined amount of benzoxazine and dicyclopentadiene-modified phenol in a solvent such as toluene, methyl ethyl ketone, and acetone to obtain a solution state. And a method of distilling off the solvent after mixing the two.
本発明の熱硬化性樹脂組成物は、例えば１８０℃以上で１〜１０時間加熱すれば、その硬化物を得ることができる。 If the thermosetting resin composition of the present invention is heated at, for example, 180 ° C. or more for 1 to 10 hours, the cured product can be obtained.
本発明では、上記の熱硬化性樹脂組成物に、その特性を損なわない範囲で各種の樹脂およびフイラーを含ませることができる。他の樹脂としては、例えば、ノボラック、レゾール、エポキシ樹脂、ポリイミド樹脂などの各種熱熱硬化性樹脂、例えば、ポリカーボネート、シリコーン樹脂などの各種熱可塑性樹脂が挙げられる。また、各種フイラーとしては、シリカ、炭素粉、マイカ、タルク、炭素繊維、有機繊維などが挙げられる。これらは、目的に応じて適宜組み合わせて、適量添加することができる。 In the present invention, various resins and fillers can be included in the thermosetting resin composition as long as the characteristics are not impaired. Examples of the other resin include various thermo-thermosetting resins such as novolac, resol, epoxy resin, and polyimide resin, and various thermoplastic resins such as polycarbonate and silicone resin. Examples of various fillers include silica, carbon powder, mica, talc, carbon fiber, and organic fiber. These can be appropriately combined and added in an appropriate amount according to the purpose.
このような他の成分のうちでも、たとえば、ノボラック樹脂を、熱硬化性樹脂組成物全量１００質量％に対し０.１〜３０質量％含有することが好ましい。
このような量でノボラック樹脂を含むと、硬化速度と硬化物耐熱性の両方に優れた熱硬化性樹脂組成物が得られるからである。
Among such other components, for example, the novolak resin is preferably contained in an amount of 0.1 to 30% by mass relative to 100% by mass of the total amount of the thermosetting resin composition.
This is because when the novolak resin is contained in such an amount, a thermosetting resin composition excellent in both the curing speed and the heat resistance of the cured product can be obtained.
また、シリカを、熱硬化性樹脂組成物全量１００質量％に対し１〜９０質量％含有することも好ましい。
このような量でシリカを含むと、機械的強度と耐熱性の両方に優れた熱硬化性樹脂組成物が得られるからである。
以下、本発明を実施例により具体的に説明する。
Moreover, it is also preferable to contain 1-90 mass% of silica with respect to 100 mass% of thermosetting resin composition whole quantity.
This is because when silica is contained in such an amount, a thermosetting resin composition excellent in both mechanical strength and heat resistance can be obtained.
Hereinafter, the present invention will be specifically described by way of examples.
（合成例１）ベンゾオキサジンの合成
攪拌装置、温度計、還流装置、不活性ガス導入管、オイルバスを備えた１リットルの反応容器（セパラブルフラスコ）に、４，４’−オキシジアニリン１０５ｇ、パラホルムアルデヒド６９ｇ、溶媒としてトルエン４００ｇを挿入して、窒素を流しながら９０℃に加熱した。
加熱終了後、予め、９０℃に加熱したフェノールを９９ｇ挿入し、更に１１０℃に加熱して３時間反応させた。その後、１７０℃に昇温して溶媒のトルエンを減圧蒸留し、ベンゾオキサジン２２０ｇを得た。
得られたベンゾオキサジンを粉砕機で微粉にした。
Synthesis Example 1 Synthesis of benzoxazine
In a 1 liter reaction vessel (separable flask) equipped with a stirrer, thermometer, reflux device, inert gas inlet tube, oil bath, 105 g of 4,4′-oxydianiline, 69 g of paraformaldehyde, 400 g of toluene as a solvent And heated to 90 ° C. with flowing nitrogen.
After the heating was completed, 99 g of phenol heated to 90 ° C. was inserted in advance, and further heated to 110 ° C. for 3 hours. Thereafter, the temperature was raised to 170 ° C. and the solvent toluene was distilled under reduced pressure to obtain 220 g of benzoxazine.
The obtained benzoxazine was pulverized with a pulverizer.
（合成例２）ジシクロペンタジエン変性フェノールの合成
攪拌装置、温度計、還流装置、不活性ガス導入管、オイルバスを備えた１リットルの反応容器（セパラブルフラスコ）にフェノール（和光純薬製）２７８ｇ（２.９ｍｏｌ）を仕込んで８０℃に加熱した。
加熱終了後、三フッ化ホウ素フェノール錯体（和光純薬製）２.５ｇを添加し、更に、１４０℃に昇温して、ジシクロペンタジエン（和光純薬製）１００ｇ（０.７６ｍｏｌ）を２時間かけて徐々に添加した。添加が終了したら水酸化カルシウム（和光純薬製）７.５ｇと活性炭素（和光純薬製）２.５ｇを添加して３０分攪拌した。
攪拌終了後、反応混合物をろ過した。回収したろ液は、減圧蒸留ができる容器に移し、２２０℃に昇温して、減圧蒸留を行ない未反応のフェノールを蒸留除去した。
蒸留残渣を回収し、２２０ｇのジシクロペンタジエン変性フェノールを得た。
得られたジシクロペンタジエン変性フェノールを粉砕機で微粉にした。
(Synthesis Example 2) Synthesis of dicyclopentadiene-modified phenol Phenol (manufactured by Wako Pure Chemical Industries) in a 1-liter reaction vessel (separable flask) equipped with a stirrer, thermometer, refluxing device, inert gas introduction tube, and oil bath 278 g (2.9 mol) was charged and heated to 80 ° C.
After completion of heating, 2.5 g of boron trifluoride phenol complex (Wako Pure Chemical Industries, Ltd.) was added, and the temperature was further raised to 140 ° C., and dicyclopentadiene (Wako Pure Chemical Industries, Ltd.) 100 g (0.76 mol) was added. Gradually added over time. When the addition was completed, 7.5 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries) and 2.5 g of activated carbon (manufactured by Wako Pure Chemical Industries) were added and stirred for 30 minutes.
After completion of stirring, the reaction mixture was filtered. The collected filtrate was transferred to a container capable of distillation under reduced pressure, heated to 220 ° C., and distilled under reduced pressure to remove unreacted phenol.
The distillation residue was recovered to obtain 220 g of dicyclopentadiene-modified phenol.
The obtained dicyclopentadiene-modified phenol was pulverized with a pulverizer.
（実施例１）
上記で得られたベンゾオキサジン９ｇ、ジシクロペンタジエン変性フェノール１ｇをミキサーで混合した。混合物を、アルミ製カップに入れて２００℃に加熱し、溶融させてアルミ製スプーンを用いて十分に混練して均一化して熱硬化性樹脂組成物を得た。
＜硬化試験＞
次いで、上記組成物を硬化温度２５０℃に加熱し、硬化時間を様々に変えて硬化サンプルを作成した。各サンプルのＤＳＣ測定を行なって、発熱ピークの面積から発熱量を測定した。所定硬化時間における硬化率を、１式より算出した。硬化率と硬化時間の関係を図１に示す。
Example 1
9 g of the benzoxazine obtained above and 1 g of dicyclopentadiene-modified phenol were mixed with a mixer. The mixture was put in an aluminum cup, heated to 200 ° C., melted, sufficiently kneaded using an aluminum spoon, and homogenized to obtain a thermosetting resin composition.
<Curing test>
Next, the composition was heated to a curing temperature of 250 ° C., and curing samples were prepared by varying the curing time. DSC measurement of each sample was performed, and the calorific value was measured from the area of the exothermic peak. The curing rate at a predetermined curing time was calculated from one formula. The relationship between the curing rate and the curing time is shown in FIG.
（比較例１）
合成例１で得られたベンゾオキサジン単独（ジシクロペンタジエン変性フェノールを添加せず）で実施例１と同様の硬化試験を行った。結果を図１に示す。
(Comparative Example 1)
The same curing test as in Example 1 was performed with benzoxazine alone (without adding dicyclopentadiene-modified phenol) obtained in Synthesis Example 1. The results are shown in FIG.
（実施例２）
実施例１において、混合比を、ベンゾオキサジン６ｇ、ジシクロペンタジエン変性フェノール４ｇに変えた以外は、同様の硬化試験を行った。結果を図１に示す。
(Example 2)
In Example 1, the same curing test was conducted except that the mixing ratio was changed to 6 g of benzoxazine and 4 g of dicyclopentadiene-modified phenol. The results are shown in FIG.
（実施例３）
実施例１において、混合比を、ベンゾオキサジン９.７ｇ、ジシクロペンタジエン変性フェノール０.３ｇに変えた以外は、同様の硬化試験を行った。結果を図１に示す。
(Example 3)
A similar curing test was conducted except that the mixing ratio in Example 1 was changed to 9.7 g of benzoxazine and 0.3 g of dicyclopentadiene-modified phenol. The results are shown in FIG.
（合成例３）ベンゾオキサジンの合成
４，４’−オキシジアニリン１０５ｇの代わりに、４，４’−ジアミノジフェニルメタン１０５ｇを用いた以外は、合成例１と同様にしてベンゾオキサジンを得た。
Synthesis Example 3 Synthesis of benzoxazine
Benzoxazine was obtained in the same manner as in Synthesis Example 1 except that 105 g of 4,4′-diaminodiphenylmethane was used instead of 105 g of 4,4′-oxydianiline.
（実施例４）
実施例１において、ベンゾオキサジンを合成例３で得られたものに代えた以外は、同様の硬化試験を行った。結果を図２に示す。
Example 4
A similar curing test was performed in Example 1 except that benzoxazine was replaced with that obtained in Synthesis Example 3. The results are shown in FIG.
（比較例２）
合成例３で得られたベンゾオキサジン単独で実施例１と同様の硬化試験を行った。結果を図２に示す。
(Comparative Example 2)
The same curing test as in Example 1 was performed using benzoxazine alone obtained in Synthesis Example 3. The results are shown in FIG.
（実施例５）
実施例１と同様に作成したベンゾオキサジンとジシクロペンタジエン変性フェノールの混合物９ｇ、ノボラック樹脂（群栄化学製ＰＳＭ−４２６１）１ｇをミキサーで混合した。混合物をアルミ製カップに入れて２００℃に加熱して溶融させ、ステンレス製スプーンを用いて十分に混練して均一化した。実施例１と同様の硬化試験を行った。結果を図３に示す。
(Example 5)
9 g of a mixture of benzoxazine and dicyclopentadiene-modified phenol prepared in the same manner as in Example 1 and 1 g of novolak resin (PSM-4261 manufactured by Gunei Chemical Co., Ltd.) were mixed with a mixer. The mixture was put in an aluminum cup, heated to 200 ° C. to melt, and sufficiently kneaded and homogenized using a stainless steel spoon. The same curing test as in Example 1 was performed. The results are shown in FIG.
（比較例３）
熱硬化性樹脂組成物９ｇに代えて合成例１で得られたベンゾオキサジンサジン９ｇを、ノボラック樹脂と混合した以外は実施例５と同様にして熱硬化性組成物の方法で混練して均一化した。実施例１と同様の硬化試験を行った。結果を図３に示す。
(Comparative Example 3)
9 g of benzoxazine sazine obtained in Synthesis Example 1 instead of 9 g of thermosetting resin composition was kneaded and homogenized in the same manner as in Example 5 except that it was mixed with novolak resin. did. The same curing test as in Example 1 was performed. The results are shown in FIG.
（実施例６）
実施例１と同様に作成したベンゾオキサジンとジシクロペンタジエン変性フェノールの混合物５ｇ、シリカ粉５ｇをミキサーで混合した。この混合物をアルミ製カップに入れて、２００℃に加熱して溶融させ、ステンレス製スプーンを用いて十分に混練して均一化した。実施例１と同様の硬化試験を行った。結果を図４に示す。
(Example 6)
5 g of a mixture of benzoxazine and dicyclopentadiene-modified phenol prepared in the same manner as in Example 1 and 5 g of silica powder were mixed with a mixer. This mixture was put in an aluminum cup, heated to 200 ° C. to be melted, and sufficiently kneaded and homogenized using a stainless steel spoon. The same curing test as in Example 1 was performed. The results are shown in FIG.
（比較例４）
合成例１で得られたベンゾオキサジン５ｇ、シリカ粉５ｇを実施例６と同様の方法で混練して均一化した。実施例１と同様の硬化試験を行った。図４に示した。
(Comparative Example 4)
Benzoxazine 5 g and silica powder 5 g obtained in Synthesis Example 1 were kneaded and homogenized in the same manner as in Example 6. The same curing test as in Example 1 was performed. This is shown in FIG.
これら図より、ベンゾオキサジンとジシクロペンタジエン変性フェノールからなる本発明実施例の組成物は、比較例の組成物に比べて、硬化速度が著しく速い。本発明の組成物により、従来、硬化速度が遅く、生産性に問題のあったベンゾオキサジン硬化物を高い生産性で製造することが可能となる。本発明の組成物を硬化させた硬化物は、耐熱性、難燃性、に優れるため、半導体封止剤やプリント配線基板積層板、成形材料などとして有用である。 From these figures, the composition of the examples of the present invention consisting of benzoxazine and dicyclopentadiene-modified phenol has a significantly faster curing rate than the composition of the comparative example. According to the composition of the present invention, it is possible to produce a benzoxazine cured product having a low curing rate and a problem in productivity with high productivity. Since the cured product obtained by curing the composition of the present invention is excellent in heat resistance and flame retardancy, it is useful as a semiconductor encapsulant, a printed wiring board laminate, a molding material, and the like.
Claims (4)
ジシクロペンタジエン変性フェノール：５０〜１質量％
を含有する熱硬化性樹脂組成物。 Benzoxazine: 50-99% by mass, and dicyclopentadiene-modified phenol: 50-1% by mass
Containing thermosetting resin composition.
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| JP2015535865A (en) * | 2013-08-23 | 2015-12-17 | 台光電子材料（昆山）有限公司Ｅｌｉｔｅ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌ （Ｋｕｎｓｈａｎ） Ｃｏ． Ｌｔｄ | Resin composition and copper-clad laminate and printed circuit board using the same |
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| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
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| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN110818868B (en) * | 2019-11-29 | 2023-12-12 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer, monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer resin and preparation method of monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer |
| JP2022108705A (en) * | 2021-01-13 | 2022-07-26 | 南亞塑膠工業股▲分▼有限公司 | Benzoxazine resin, production method of the same, and resin composition |
| JP7209763B2 (en) | 2021-01-13 | 2023-01-20 | 南亞塑膠工業股▲分▼有限公司 | Benzoxazine resin, method for producing the same, and resin composition |
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