JP2012036318A - Thermosetting resin - Google Patents
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本発明は、ポリベンゾオキサジン樹脂の反応性末端を封止した、溶媒に溶解した際の保存安定性に優れた熱硬化性樹脂に関する。 The present invention relates to a thermosetting resin having a reactive end of a polybenzoxazine resin sealed and excellent in storage stability when dissolved in a solvent.
現在、エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ウレタン樹脂等の熱硬化性樹脂は、その熱硬化性という性質に基づき、耐水性、耐薬品性、耐熱性、機械強度、信頼性などに優れ、それぞれの特性に合った分野へ応用されている。最近、電子製品や自動車、航空機、建築部材等において、高性能化、高機能化が急速に進んでいる。それに伴い、それらに使用される熱硬化性樹脂においても、今までよりも、種々の特性や安定性、信頼性などの要求が高いものとなっている。 Currently, thermosetting resins such as epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, urethane resin are based on their thermosetting properties, water resistance, chemical resistance, heat resistance, mechanical strength. It has excellent reliability and is applied to fields that match each characteristic. In recent years, electronic products, automobiles, aircraft, building materials, and the like have been rapidly increasing in performance and functionality. Along with that, thermosetting resins used for them have higher requirements such as various characteristics, stability and reliability than before.
近年、ベンゾオキサジン環を有する樹脂は開環反応性を有しているため硬化時の発生ガスが無く、硬化収縮性が低く、その硬化物は、従来のフェノール樹脂の硬化物に比較して、耐熱性、難燃性を保持しているため、ベンゾオキサジン環を有する樹脂の開発が進められている。さらに開環反応後の硬化物では、熱膨張性、吸水性、誘電特性等に優れていることから、今後、電子材料、接着剤、ＦＲＰのマトリクス樹脂、精密機械部品等への利用が期待されている。 In recent years, since the resin having a benzoxazine ring has ring-opening reactivity, there is no generated gas at the time of curing, the curing shrinkage is low, and the cured product is compared with a cured product of a conventional phenol resin, Development of a resin having a benzoxazine ring is underway because it retains heat resistance and flame retardancy. Furthermore, the cured product after the ring-opening reaction is excellent in thermal expansion, water absorption, dielectric properties, etc., and is expected to be used for electronic materials, adhesives, FRP matrix resins, precision machine parts, etc. in the future. ing.
代表的な低分子量体のベンゾオキサジン化合物として、一般式（Ｉ）〜（ＩＩＩ）に示すような化合物が提案されている（例えば、特許文献１、特許文献２、及び特許文献３参照。）。しかし、これらの低分子量体のベンゾオキサジン化合物の開環反応による硬化物は、従来のフェノール樹脂と比較して、寸法安定性に優れるものの、フェノール樹脂の硬化物と同様に非常に脆いという欠点がある。 As typical low molecular weight benzoxazine compounds, compounds represented by the general formulas (I) to (III) have been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, the cured product obtained by the ring-opening reaction of these low molecular weight benzoxazine compounds is excellent in dimensional stability as compared with the conventional phenol resin, but has the disadvantage that it is very brittle like the cured product of the phenol resin. is there.
このため、ヒドロキシフェニル基を二つ有するフェノール類、ジアミン類及びホルムアルデヒド等から合成される主鎖にベンゾオキサジン環構造を有するポリベンゾオキサジン樹脂が提案されている（例えば、特許文献４及び非特許文献１参照。）。低分子量体のベンゾオキサジン化合物と比較して、これらのポリベンゾオキサジン樹脂は硬化物の脆さが改善され、さらに耐熱性、難燃性、熱膨張率、引張強度、フィルム成形能等に優れていることが示されている。 For this reason, polybenzoxazine resins having a benzoxazine ring structure in the main chain synthesized from phenols having two hydroxyphenyl groups, diamines and formaldehyde have been proposed (for example, Patent Document 4 and Non-Patent Documents). 1). Compared with low-molecular-weight benzoxazine compounds, these polybenzoxazine resins have improved brittleness of cured products, and are excellent in heat resistance, flame retardancy, thermal expansion coefficient, tensile strength, film moldability, etc. It has been shown that
しかしながら、特許文献４及び非特許文献１記載のポリベンゾオキサジン樹脂は、溶媒に溶解した際の保存安定性が悪く、早期にゲル化してしまう。特にトルエン、キシレン等の非極性溶媒やクロロホルム等のハロゲン系溶媒に溶解させた溶液状態での保存安定性が悪く、中でもクロロホルム等のハロゲン系溶媒が非常にゲル化の進行が早い。この理由としては、ポリベンゾオキサジン樹脂の末端が、反応性の高いアミノ基やアミノメチロール基、あるいはベンゾオキサジン環の開環促進効果があるフェノール性水酸基が存在することによるものと考えられる。
本発明は、溶媒に溶解した際の保存安定性に優れた、ベンゾオキサジン環構造を主鎖中に有する熱硬化性樹脂を提供することを目的とする。
However, the polybenzoxazine resins described in Patent Document 4 and Non-Patent Document 1 have poor storage stability when dissolved in a solvent, and gel early. In particular, the storage stability in a solution state dissolved in a nonpolar solvent such as toluene or xylene or a halogen-based solvent such as chloroform is poor, and in particular, a halogen-based solvent such as chloroform proceeds very rapidly. The reason for this is considered to be that the terminal of the polybenzoxazine resin is a highly reactive amino group, aminomethylol group, or phenolic hydroxyl group that has an effect of promoting the opening of the benzoxazine ring.
An object of the present invention is to provide a thermosetting resin having a benzoxazine ring structure in the main chain, which is excellent in storage stability when dissolved in a solvent.
本発明は、以下の構成を有する。
［１］下記式（１）で表わされるベンゾオキサジン環構造を主鎖中に有するポリベンゾオキサジン樹脂の反応性末端の一部または全部を封止した熱硬化性樹脂。
（式（１）において、Ａｒ１は芳香族基を示し、Ｒ１は有機基を示し、ｎは２以上の整数を示す。）
The present invention has the following configuration.
[1] A thermosetting resin in which a part or all of the reactive ends of a polybenzoxazine resin having a benzoxazine ring structure represented by the following formula (1) in the main chain is sealed.
(In Formula (1), Ar 1 represents an aromatic group, R 1 represents an organic group, and n represents an integer of 2 or more.)
［２］前記ポリベンゾオキサジン樹脂が、ヒドロキシフェニル基を二つ有するフェノール類と、ジアミン類と、アルデヒド類とを原料として用いて製造したことを特徴とする［１］に記載の熱硬化性樹脂。 [2] The thermosetting resin according to [1], wherein the polybenzoxazine resin is produced using phenols having two hydroxyphenyl groups, diamines, and aldehydes as raw materials. .
［３］前記反応性末端の封止方法が、アセチル化、ベンゾイル化、メチル化、ベンジル化、ｔｅｒｔ−ブチル化、ｐ−メトキシベンジル化、トリメチルシリル化、トリエチルシリル化、メトキシメチル化、メトキシエトキシメチル化からなる群から選択される１種以上の反応である［１］または［２］記載の熱硬化性樹脂。 [3] The reactive terminal sealing method is acetylation, benzoylation, methylation, benzylation, tert-butylation, p-methoxybenzylation, trimethylsilylation, triethylsilylation, methoxymethylation, methoxyethoxymethyl. The thermosetting resin according to [1] or [2], which is one or more reactions selected from the group consisting of:
本発明によれば、ベンゾオキサジン環構造を主鎖中に有し、溶媒に溶解した際の保存安定性に優れた熱硬化性樹脂が提供される。 According to the present invention, there is provided a thermosetting resin having a benzoxazine ring structure in the main chain and having excellent storage stability when dissolved in a solvent.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明に係る熱硬化性樹脂は、上記式（１）で表わされるベンゾオキサジン環構造を主鎖中に有するポリベンゾオキサジン樹脂の反応性末端を封止することにより得られる。
まずは上記ポリベンゾオキサジン樹脂について説明する。
上記ポリベンゾオキサジン樹脂は、ヒドロキシフェニル基を二つ有するフェノール類とジアミン類とアルデヒド類とを有機溶媒中において反応させ、製造するものである。
The thermosetting resin according to the present invention is obtained by sealing the reactive terminal of a polybenzoxazine resin having a benzoxazine ring structure represented by the above formula (1) in the main chain.
First, the polybenzoxazine resin will be described.
The polybenzoxazine resin is produced by reacting phenols having two hydroxyphenyl groups, diamines and aldehydes in an organic solvent.
上記ヒドロキシフェニル基を二つ有するフェノール類は、下記式（２）で表され、ヒドロキシフェニル基の水酸基と結合する炭素に対して、少なくとも一方のオルソ位に置換可能な水素を有するものであれば、特に限定されない。（式（２）において、Ａｒ１は芳香族基を示す。）
ヒドロキシフェニル基を二つ有するフェノール類としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールＥ、ビスフェノールＺ、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ビフェノール、４，４’−ジヒドロキシベンゾフェノン、４，４’−［１，３−フェニレンビス（１−メチル−エチリデン）］ビスフェノール（三井化学ファイン製「ビスフェノールＭ」）、４，４’−［１，４−フェニレンビス（１−メチル−エチリデン）］ビスフェノール（三井化学ファイン製「ビスフェノールＰ」）等が挙げられ、中でも、ビスフェノールＡ、ビスフェノールＦが安価であることから好ましい。これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
The phenols having two hydroxyphenyl groups are represented by the following formula (2) and have a hydrogen that can be substituted in at least one ortho position with respect to carbon bonded to the hydroxyl group of the hydroxyphenyl group. There is no particular limitation. (In Formula (2), Ar 1 represents an aromatic group.)
Examples of phenols having two hydroxyphenyl groups include bisphenol A, bisphenol F, bisphenol S, bisphenol E, bisphenol Z, 4,4′-dihydroxydiphenyl ether, 4,4′-biphenol, 4,4′-dihydroxybenzophenone, 4,4 ′-[1,3-phenylenebis (1-methyl-ethylidene)] bisphenol (“Bisphenol M” manufactured by Mitsui Chemicals Fine), 4,4 ′-[1,4-phenylenebis (1-methyl-ethylidene) )] Bisphenol (“Bisphenol P” manufactured by Mitsui Chemicals Fine) and the like, among which bisphenol A and bisphenol F are preferable because they are inexpensive. These may be used individually by 1 type and may be used in combination of 2 or more type.
上記ジアミン類は、下記式（３）で表され、芳香族ジアミン、脂肪族ジアミン、脂環式ジアミン等、両末端にアミノ基を有するものであれば、特に限定されない。（式（３）において、Ｒ１は有機基を示す。）
芳香族ジアミンとしては、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、２，２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、４，４’−［１，４−フェニレンビス（１−メチル−エチリデン）］ビスアニリン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン等が挙げられ、中でも、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテルが安価であることから好ましい。
また、脂肪族ジアミンとしては、エチレンジアミン、１，３−プロパンジアミン、１，４−ブタンジアミン、１，５−ペンタンジアミン、１，６−ヘキサンジアミン、１，８−オクタンジアミン、１，１０−デカンジアミン、１，１１−ウンデカンジアミン、１，１２−ドデカンジアミン、１，１８−オクタデカンジアミン等が挙げられ、中でも、エチレンジアミン、１，３−プロパンジアミン、１，６−ヘキサンジアミンが安価であることから好ましい。
さらに、その他のジアミン類として、脂環式ジアミン、不飽和や分岐した炭化水素基を持つジアミン等も使用することができる。脂環式ジアミンとしては、１，４−シクロヘキサンジアミン、１，３−シクロヘキサンジアミン、１，４−ビス（アミノメチル）シクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）、４，４’−メチレンビス（２−メチルシクロヘキシルアミン）、イソホロンジアミン、１，３−ジアミノアダマンタン、ノルボルナンジアミン等が挙げられる。
これらジアミン類は１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
これらのジアミン類の種類の組み合わせや配合割合等により、種々の物性を変化させることができる。例えば、芳香族ジアミンや脂環式ジアミンの配合割合を増加させると、硬化物の耐熱性を向上させることができ、脂環式ジアミンの配合割合を増加させると硬化物の透明性が向上し、直鎖脂肪族ジアミンの配合割合を増加させると硬化物の可とう性を向上させることができる。したがって、各種用途における要求特性に合わせたポリベンゾオキサジン樹脂を製造することが可能である。
The diamines are not particularly limited as long as they are represented by the following formula (3) and have amino groups at both ends, such as aromatic diamines, aliphatic diamines, and alicyclic diamines. (In Formula (3), R 1 represents an organic group.)
As aromatic diamines, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 ′-[1,4 -Phenylenebis (1-methyl-ethylidene)] bisaniline, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene and the like, among others, 4,4′- Diaminodiphenylmethane and 4,4′-diaminodiphenyl ether are preferred because they are inexpensive.
Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, and 1,10-decane. Examples include diamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine and the like. Among them, ethylenediamine, 1,3-propanediamine, and 1,6-hexanediamine are inexpensive. preferable.
Furthermore, as other diamines, alicyclic diamines, diamines having unsaturated or branched hydrocarbon groups, and the like can also be used. Examples of the alicyclic diamine include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4′-methylenebis ( Cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,3-diaminoadamantane, norbornanediamine, and the like.
These diamines may be used individually by 1 type, and may be used in combination of 2 or more type.
Various physical properties can be changed depending on the combination of the types of these diamines, the blending ratio, and the like. For example, increasing the blending ratio of aromatic diamine or alicyclic diamine can improve the heat resistance of the cured product, and increasing the blending ratio of alicyclic diamine improves the transparency of the cured product, Increasing the blending ratio of the linear aliphatic diamine can improve the flexibility of the cured product. Therefore, it is possible to produce a polybenzoxazine resin that meets the required characteristics in various applications.
上記アルデヒド類としては、特に限定されるものではないが、例えば、アセトアルデヒド、ホルムアルデヒド等が挙げられ、これらは１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。該ホルムアルデヒドとしては、パラホルムアルデヒドやホルムアルデヒドの水溶液が挙げられるが、合成のしやすさから、ホルムアルデヒドの水溶液が好ましい。 Although it does not specifically limit as said aldehydes, For example, acetaldehyde, formaldehyde, etc. are mentioned, These may be used individually by 1 type and may be used in combination of 2 or more type. . Examples of the formaldehyde include paraformaldehyde and an aqueous solution of formaldehyde, but an aqueous solution of formaldehyde is preferable because of ease of synthesis.
上記反応工程における、反応温度、反応時間については特に限定されないが、通常、有機溶媒中、２５〜１２０℃の範囲で数十分〜数時間反応させ、有機溶媒除去工程を行うことによりポリベンゾオキサジン樹脂を得ることができる。
ベンゾオキサジン環の生成を向上させ、ベンゾオキサジン環の開環反応を抑制させるという観点から、反応温度は５０〜９０℃、反応時間は１〜１０時間であることが好ましい。
The reaction temperature and reaction time in the above reaction step are not particularly limited. Usually, polybenzoxazine is reacted in an organic solvent in the range of 25 to 120 ° C. for several tens of minutes to several hours, and the organic solvent removal step is performed. A resin can be obtained.
From the viewpoint of improving the formation of the benzoxazine ring and suppressing the ring-opening reaction of the benzoxazine ring, the reaction temperature is preferably 50 to 90 ° C. and the reaction time is preferably 1 to 10 hours.
また、使用する有機溶媒についても特に限定されるものではないが、原料のヒドロキシフェニル基を二つ有するフェノール類やジアミン類および生成物である重合体に対して溶解性の良好なものが好ましい。このような溶媒として、例えば、クロロホルム、ジクロロメタン等のハロゲン系溶媒、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、キシレン、トルエン等の芳香族系溶媒、等が挙げられる。 Further, the organic solvent to be used is not particularly limited, but those having good solubility with respect to the starting polymer such as phenols and diamines having two hydroxyphenyl groups and the product polymer are preferable. Examples of such a solvent include halogen solvents such as chloroform and dichloromethane, ether solvents such as tetrahydrofuran and dioxane, aromatic solvents such as xylene and toluene, and the like.
このようにして得られた上記ポリベンゾオキサジン樹脂の反応性末端の封止工程について説明する。 The step of sealing the reactive end of the polybenzoxazine resin thus obtained will be described.
反応性末端の封止工程において、反応溶液中でそのまま封止する方法と、反応溶液を一度メタノール等の貧溶媒に投入することにより、樹脂成分を析出させて、これをろ過、乾燥させることにより固液分離し、再溶解後に封止する方法のいずれかで実施される。固形化せず反応溶液中で封止させる場合は、ジヒドロキシフェニル基を二つ有するフェノール類等の未反応原料を除去するため、塩基性水溶液で洗浄しておくことが有効である。 In the reactive terminal sealing step, the method of sealing as it is in the reaction solution, and the reaction solution is once poured into a poor solvent such as methanol to precipitate the resin component, which is filtered and dried. It is carried out by any of the methods of solid-liquid separation and sealing after re-dissolution. When sealing in a reaction solution without solidifying, it is effective to wash with a basic aqueous solution in order to remove unreacted raw materials such as phenols having two dihydroxyphenyl groups.
塩基性水溶液で洗浄する場合の塩基性化合物としては、特に限定されるものではないが、例えば、炭酸ナトリウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられる。 The basic compound for washing with a basic aqueous solution is not particularly limited, and examples thereof include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide.
反応性末端の封止方法としては、水酸基、アミノ基等の反応性の高い官能基を反応性の低い保護基に変換する方法を利用する。水酸基、アミノ基等の反応性の高い官能基を反応性の低い保護基に変換することができる方法であれば、特に限定されるものではないが、アセチル化、ベンゾイル化、メチル化、ベンジル化、ｔｅｒｔ−ブチル化、ｐ−メトキシベンジル化、トリメチルシリル化、トリエチルシリル化、メトキシメチル化、メトキシエトキシメチル化が好ましい。これらの封止方法は１種を選択しても、２種以上を組み合わせて選択しても良い。 As a method for sealing the reactive terminal, a method of converting a highly reactive functional group such as a hydroxyl group or an amino group into a protecting group having a low reactivity is used. The method is not particularly limited as long as it is a method capable of converting a highly reactive functional group such as a hydroxyl group or an amino group into a protective group having low reactivity, but acetylation, benzoylation, methylation, benzylation, and the like. Tert-butylation, p-methoxybenzylation, trimethylsilylation, triethylsilylation, methoxymethylation, methoxyethoxymethylation are preferred. These sealing methods may be selected from one type or a combination of two or more types.
このようにして得られた本発明の熱硬化性樹脂は、反応性末端が封止されているため、溶液状態におけるゲル化を防止することができ、溶媒に溶解した際の保存安定性に優れる。
また、反応性末端を封止する割合は、特に範囲指定されるものではなく、反応性末端の一部が封止されるだけでも、未封止の樹脂と比較して溶媒に溶解した際の保存安定性は向上し、封止割合が高いほど溶媒に溶解した際の保存安定性は向上する。
Since the thermosetting resin of the present invention thus obtained has a reactive end sealed, gelation in a solution state can be prevented, and the storage stability when dissolved in a solvent is excellent. .
In addition, the ratio for sealing the reactive terminal is not particularly specified, and even when only a part of the reactive terminal is sealed, the ratio at the time of dissolving in the solvent compared to the unsealed resin The storage stability is improved, and the higher the sealing ratio, the better the storage stability when dissolved in a solvent.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited at all by these Examples.
（ポリベンゾオキサジン樹脂（Ａ−１）の合成）
クロロホルム中に、ビスフェノールＡ３４．２ｇ（０．１５ｍｏｌ）、４，４’−ジアミノジフェニルメタン１９．８ｇ（０．１０ｍｏｌ）、１，６−ヘキサンジアミン５．８ｇ（０．０５ｍｏｌ）を投入し、５０℃に昇温した。５０％ホルムアルデヒド水溶液３６．０ｇ（０．６０ｍｏｌ）を滴下した後、３０分間攪拌した。その後、さらに昇温して還流下で７時間反応させた。反応終了後、反応溶液を多量のメタノールに投じて反応物を析出させた。その後、ろ別により反応物を分離して、メタノールで洗浄し、４０℃で減圧乾燥することによりポリベンゾオキサジン樹脂（Ａ−１）を得た。ＧＰＣによる重量平均分子量は、標準ポリスチレン換算で１２，０００であった。
(Synthesis of polybenzoxazine resin (A-1))
Into chloroform, 34.2 g (0.15 mol) of bisphenol A, 19.8 g (0.10 mol) of 4,4′-diaminodiphenylmethane, and 5.8 g (0.05 mol) of 1,6-hexanediamine were charged at 50 ° C. The temperature was raised to. After dropping 36.0 g (0.60 mol) of 50% aqueous formaldehyde solution, the mixture was stirred for 30 minutes. Thereafter, the temperature was further raised and the reaction was carried out under reflux for 7 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol to precipitate the reaction product. Thereafter, the reaction product was separated by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. to obtain a polybenzoxazine resin (A-1). The weight average molecular weight by GPC was 12,000 in terms of standard polystyrene.
［実施例１］
（ポリベンゾオキサジン樹脂（Ａ−１）のアセチル化）
ポリベンゾオキサジン樹脂（Ａ−１）２０ｇをピリジン７０ｇに溶解させ、さらに無水酢酸１０ｇを添加し、室温で１２時間攪拌した。この溶液を多量のメタノールに投じて反応物を析出させた。その後、ろ別により反応物を分離して、メタノールで洗浄し、４０℃で減圧乾燥することにより、熱硬化性樹脂を得た。得られた熱硬化性樹脂を１３Ｃ−ＮＭＲにて測定したところ、１６９ｐｐｍ付近にアセチル基由来のカルボニル炭素のピークが検出されたことから、アセチル化されていること確認した。
[Example 1]
(Acetylation of polybenzoxazine resin (A-1))
20 g of polybenzoxazine resin (A-1) was dissolved in 70 g of pyridine, 10 g of acetic anhydride was further added, and the mixture was stirred at room temperature for 12 hours. This solution was poured into a large amount of methanol to precipitate the reaction product. Thereafter, the reaction product was separated by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. to obtain a thermosetting resin. When the obtained thermosetting resin was measured by 13C-NMR, it was confirmed that acetylation was observed because a peak of carbonyl carbon derived from an acetyl group was detected in the vicinity of 169 ppm.
［実施例２］
（ポリベンゾオキサジン樹脂（Ａ−１）のベンジル化）
ポリベンゾオキサジン樹脂（Ａ−１）２０ｇ、ベンジルクロライド１０ｇ、テトラブチルアンモニウムブロマイド０．２ｇをクロロホルム８０ｇに溶解させた後、８０℃に昇温する。この溶液に４９％水酸化ナトリウム水溶液１０ｇを滴下し、８０℃で４時間攪拌した。次に、この溶液を１０％塩酸水溶液で中和した後、多量のメタノールに投じて反応物を析出させた。その後、ろ別により反応物を分離して、メタノールで洗浄し、４０℃で減圧乾燥することにより、熱硬化性樹脂を得た。得られた熱硬化性樹脂を１３Ｃ−ＮＭＲにて測定したところ、５０ｐｐｍおよび７０ｐｐｍ付近にベンジル基由来のメチレン炭素のピークが検出されたことから、樹脂がベンジル化されていること確認した。
[Example 2]
(Benzylation of polybenzoxazine resin (A-1))
After dissolving 20 g of polybenzoxazine resin (A-1), 10 g of benzyl chloride, and 0.2 g of tetrabutylammonium bromide in 80 g of chloroform, the temperature is raised to 80 ° C. To this solution, 10 g of a 49% aqueous sodium hydroxide solution was added dropwise and stirred at 80 ° C. for 4 hours. Next, this solution was neutralized with a 10% aqueous hydrochloric acid solution, and then poured into a large amount of methanol to precipitate a reaction product. Thereafter, the reaction product was separated by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. to obtain a thermosetting resin. When the obtained thermosetting resin was measured by 13C-NMR, the peak of methylene carbon derived from a benzyl group was detected in the vicinity of 50 ppm and 70 ppm, and it was confirmed that the resin was benzylated.
［比較例１］
上記に示したポリベンゾオキサジン樹脂（Ａ−１）を比較用の熱硬化性樹脂とした。
[Comparative Example 1]
The polybenzoxazine resin (A-1) shown above was used as a comparative thermosetting resin.
実施例１、実施例２および比較例１で得られた熱硬化性樹脂について、それぞれ溶媒に溶解した際の保存安定性の評価を行った。 The thermosetting resins obtained in Example 1, Example 2 and Comparative Example 1 were evaluated for storage stability when dissolved in a solvent.
［保存安定性の評価］
熱硬化性樹脂１ｇとクロロホルム３ｇを直径１０ｍｍの試験管に入れて溶解させ、２５質量％の溶液を作製した。その後、試験管を密閉し、２５℃の条件下にて静置した。１日ごとに試験管を逆さにして１分経過後、液がたれてこない状態になった日数を、表１に示した。
なお、日数が長いほど、溶媒に溶解した際の保存安定性が良好なことを示す。
[Evaluation of storage stability]
1 g of thermosetting resin and 3 g of chloroform were put into a test tube having a diameter of 10 mm and dissolved to prepare a 25% by mass solution. Thereafter, the test tube was sealed and allowed to stand at 25 ° C. Table 1 shows the number of days in which the test tube was inverted every day and the liquid did not sag after 1 minute.
The longer the number of days, the better the storage stability when dissolved in a solvent.
表１より、反応性末端が封止された本発明の熱硬化性樹脂である実施例１及び２は１０日経過した状態でも流動性が有り、保存安定性が良い。
一方反応性末端が封止されていない比較例１では３日経過した時点で流動性が無くなり、保存安定性が悪い。
From Table 1, Examples 1 and 2, which are thermosetting resins of the present invention with the reactive ends sealed, have fluidity even after 10 days and have good storage stability.
On the other hand, in Comparative Example 1 in which the reactive terminal is not sealed, the fluidity is lost after 3 days and the storage stability is poor.
Claims (3)
（式（１）において、Ａｒ１は芳香族基を示し、Ｒ１は有機基を示し、ｎは２以上の整数を示す。）
(In Formula (1), Ar 1 represents an aromatic group, R 1 represents an organic group, and n represents an integer of 2 or more.)
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