JP2009286888A - Thermosetting resin composition, thermosetting resin molding material, and cured product of the same - Google Patents
Thermosetting resin composition, thermosetting resin molding material, and cured product of the same Download PDFInfo
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Abstract
Description
本発明は、熱硬化性樹脂組成物、熱硬化性樹脂成形材料及びその硬化物に関するものである。 The present invention relates to a thermosetting resin composition, a thermosetting resin molding material, and a cured product thereof.
フェノール樹脂は、耐熱性、機械的強度及び電気特性等の種々の優れた特性を有しており、従来より、成形材料、積層板及び接着剤等の種々の用途に使用されている。 Phenolic resins have various excellent properties such as heat resistance, mechanical strength, and electrical properties, and are conventionally used in various applications such as molding materials, laminates, and adhesives.
フェノール樹脂には、レゾール型フェノール樹脂とノボラック型フェノール樹脂の２種類がある。これらの内、ノボラック型フェノール樹脂は、硬化剤を用いて、加熱して硬化させる。このような硬化剤としては、一般的にヘキサメチレンテトラミンが使用されているが、硬化反応において、副生成物として縮合水の他、アンモニアを生成することが知られている。そのため、硬化剤としてのヘキサメチレンテトラミンに替えて、レゾール型フェノール樹脂を用いることが検討されている（例えば、特許文献１参照）。しかしながら、アンモニアの生成を抑制するとともに、さらに硬化物における耐熱性や機械強度などの特性の向上が求められていた。 There are two types of phenolic resins: resol type phenolic resins and novolac type phenolic resins. Among these, the novolac type phenol resin is cured by heating using a curing agent. As such a curing agent, hexamethylenetetramine is generally used, but it is known that ammonia is generated in addition to condensed water as a by-product in the curing reaction. Therefore, it has been studied to use a resol type phenol resin instead of hexamethylenetetramine as a curing agent (for example, see Patent Document 1). However, while suppressing the production | generation of ammonia, the improvement of characteristics, such as heat resistance in a hardened | cured material and mechanical strength, was calculated | required.
本発明は、極めて優れた耐熱性を有する硬化物が得られる熱硬化性樹脂組成物、及びそれを用いた熱硬化性樹脂成形材料、更にはその硬化物を提供するものである。 The present invention provides a thermosetting resin composition from which a cured product having extremely excellent heat resistance can be obtained, a thermosetting resin molding material using the same, and a cured product thereof.
本発明者等は、硬化剤として一般式（１）で表される構造を有するものを用いることにより、従来のレゾール型フェノール樹脂では達成できなかった極めて優れた耐熱性を有することを見出し、更に検討を進めることにより、本発明を完成するに至った。 The present inventors have found that by using a curing agent having a structure represented by the general formula (1), it has extremely excellent heat resistance that could not be achieved by a conventional resol type phenolic resin. By proceeding with the study, the present invention has been completed.
即ち本発明は、下記第（１）項〜第（４）項により達成される。
（１） ノボラック型フェノール樹脂（ａ）及び一般式(１)で表される構造を有する硬化剤（ｂ）を含む熱硬化性樹脂組成物。
That is, the present invention is achieved by the following items (1) to (4).
(1) A thermosetting resin composition comprising a novolac-type phenolic resin (a) and a curing agent (b) having a structure represented by the general formula (1).
（２） 前記硬化剤(ｂ)は、一般式（１）におけるＡｒとして、式(２)で表される基の中から選ばれる芳香族基を有するものである第（１）項に記載の熱硬化性樹脂組成物。 (2) The curing agent (b) has an aromatic group selected from the group represented by the formula (2) as Ar in the general formula (1). Thermosetting resin composition.
（３） 第（１）項又は第（２）項に記載の熱硬化性樹脂組成物と、充填材を含む、熱硬化性樹脂成形材料。
（４） 第（１）項もしくは第（２）項に記載の熱硬化性樹脂組成物又は第（３）項に記載の熱硬化性樹脂成形材料を加熱硬化して得られる硬化物。
(3) A thermosetting resin molding material comprising the thermosetting resin composition according to item (1) or (2) and a filler.
(4) A cured product obtained by heat curing the thermosetting resin composition according to item (1) or (2) or the thermosetting resin molding material according to item (3).
本発明によれば、極めて優れた耐熱性を有する硬化物が得られる熱硬化性樹脂組成物を提供できる。また、これを用いた熱硬化性成形材料の硬化物も耐熱性に優れるものとなる。 According to the present invention, it is possible to provide a thermosetting resin composition from which a cured product having extremely excellent heat resistance can be obtained. Further, a cured product of a thermosetting molding material using the same is also excellent in heat resistance.
本発明は、ノボラック型フェノール樹脂（ａ）及び一般式（１）で表される構造を有する硬化剤（ｂ）を含む熱硬化性樹脂組成物であり、このような組成物とすることにより、極めて優れた耐熱性を有する硬化物が得られる熱硬化性樹脂組成物を提供できる。
また、本発明は、前記熱硬化性樹脂組成物及び充填材を含む熱硬化性樹脂成形材料である。
The present invention is a thermosetting resin composition containing a novolac-type phenolic resin (a) and a curing agent (b) having a structure represented by the general formula (1). By using such a composition, It is possible to provide a thermosetting resin composition from which a cured product having extremely excellent heat resistance can be obtained.
Moreover, this invention is a thermosetting resin molding material containing the said thermosetting resin composition and a filler.
本発明に用いるノボラック型フェノール樹脂（ａ）としては、一般的なノボラック型フェノール樹脂の製造方法により得られるものであれば良く、フェノール化合物とアルデヒド化合物とを、無触媒または触媒存在下で反応させて得られる樹脂が挙げられる。具体的には、フェノール樹脂、クレゾール樹脂、キシレノール樹脂およびナフトール樹脂などが挙げられ、これらの樹脂の構造としては、ランダムノボラック型でもハイオルソノボラック型でも用いることができる。 The novolak-type phenol resin (a) used in the present invention may be any one obtained by a general method for producing a novolak-type phenol resin, and a phenol compound and an aldehyde compound are reacted in the absence of a catalyst or in the presence of a catalyst. Resin obtained in this way. Specific examples include phenol resins, cresol resins, xylenol resins, and naphthol resins. The structures of these resins can be either random novolak type or high ortho novolak type.
前記フェノール化合物としては、フェノール、クレゾール、キシレノールおよびナフトールなどが挙げられる。また、前記アルデヒド化合物としては、ホルムアルデヒド及びパラホルムアルデヒド、更にはポリアセタールなどのアルデヒド源となる化合物などが挙げられる。これらの中でも、熱硬化性樹脂組成物として、最も硬化速度を速くする上で、ノボラック型フェノール樹脂（ａ）は、フェノールとホルムアルデヒドを用いて反応させて得られるノボラック型フェノール・ホルムアルデヒド樹脂が好ましい。 Examples of the phenol compound include phenol, cresol, xylenol, and naphthol. Examples of the aldehyde compound include formaldehyde and paraformaldehyde, and compounds that serve as aldehyde sources such as polyacetal. Among these, as the thermosetting resin composition, the novolak type phenol resin (a) is preferably a novolak type phenol / formaldehyde resin obtained by reacting with phenol and formaldehyde in order to increase the curing speed most.
本発明に用いる一般式（１）で表される構造を有する硬化剤（ｂ）は、水酸基とヒドロキシメチル基とを有するベンゼン環と、芳香環２つ以上で構成される芳香族基とを、メチレン基で結合した化合物である。 The curing agent (b) having a structure represented by the general formula (1) used in the present invention comprises a benzene ring having a hydroxyl group and a hydroxymethyl group, and an aromatic group composed of two or more aromatic rings. It is a compound bonded with a methylene group.
前記芳香環２つ以上で構成される芳香族基としては、ビフェニレン基、ビナフチレン基、ナフチレン基、アントラシレン基及びターフェニレン基などが挙げられる。
前記芳香環２つ以上で構成される芳香族基は、芳香環の数が多くなると融点が高くなる傾向があり、良好な成形性を発現する上で、芳香環の数が４つ以下であることが望ましい。このような観点から、芳香環２つ以上で構成される芳香族基は式(２)で表される基、即ちビフェニレン基、ナフチレン基及びアントラシレン基から選ばれることがより好ましい。
Examples of the aromatic group composed of two or more aromatic rings include a biphenylene group, a binaphthylene group, a naphthylene group, an anthracylene group, and a terphenylene group.
The aromatic group composed of two or more aromatic rings tends to have a high melting point when the number of aromatic rings increases, and the number of aromatic rings is four or less in order to develop good moldability. It is desirable. From such a viewpoint, the aromatic group composed of two or more aromatic rings is more preferably selected from the group represented by the formula (2), that is, a biphenylene group, a naphthylene group, and an anthracylene group.
硬化剤（ｂ）は、このような芳香環２つ以上で構成される芳香族基を有する構造であることにより、前記芳香環２つ以上で構成される芳香族基部分がメソゲンのように分子間相互作用で分子鎖を密に配列させ、硬化物を高強度化させる効果を得ることができると考えられる。 Since the curing agent (b) has such a structure having an aromatic group composed of two or more aromatic rings, the aromatic group portion composed of two or more aromatic rings is a molecule such as a mesogen. It is considered that the effect of increasing the strength of the cured product can be obtained by closely arranging the molecular chains by the intermolecular interaction.
さらに、一般式（１）で表される構造において、ヒドロキシメチル基の数を示すｎ及びｎ’は、１以上４以下の整数であるが、この数が多いほど硬化し易いので好ましい。 Furthermore, in the structure represented by the general formula (1), n and n ′ representing the number of hydroxymethyl groups are integers of 1 or more and 4 or less, and the larger the number, the better the curing.
本発明の熱硬化性樹脂組成物において、一般式（１）で表される構造を有する硬化剤（ｂ）を用いる量としては、前記ノボッラク型フェノール樹脂（ａ）１００重量部に対し、２０重量部以上５００重量部以下が好ましく、さらに好ましくは５０重量部以上３００重量部以下である。前記数値の範囲外でも使用できるが、前記下限値以上、上限値以下であれば、ノボラック型フェノール樹脂（ａ）及び一般式（１）で表される構造を有する硬化剤（ｂ）が、より効果的に反応し、硬化物として、ガラス転移点などの耐熱性や弾性率などの機械特性が向上する。 In the thermosetting resin composition of the present invention, the amount of the curing agent (b) having the structure represented by the general formula (1) is 20 weights with respect to 100 parts by weight of the novolak type phenol resin (a). The amount is preferably not less than 500 parts by weight and more preferably not less than 50 parts by weight and not more than 300 parts by weight. Although it can be used outside the above numerical range, the novolac-type phenol resin (a) and the curing agent (b) having a structure represented by the general formula (1) are more suitable if the lower limit value is not less than the upper limit value. It reacts effectively and as a cured product, heat resistance such as glass transition point and mechanical properties such as elastic modulus are improved.
本発明の熱硬化性樹脂組成物においてノボラック型フェノール樹脂（ａ）の硬化を促進する上で、硬化触媒を用いることができる。例えば、蓚酸、酢酸およびトリフルオロ酢酸などの有機カルボン酸；塩酸および硫酸などの無機酸；パラトルエンスルホン酸、メタンスルホン酸およびトリフルオロメタンスルホン酸などの有機スルホン酸；リン酸などの有機ホスホン酸；タングストケイ酸、タングストリン酸、モリブドケイ酸およびモリブドリン酸などのヘテロポリ酸；などを用いることができる。 In the thermosetting resin composition of the present invention, a curing catalyst can be used for accelerating the curing of the novolac type phenol resin (a). For example, organic carboxylic acids such as succinic acid, acetic acid and trifluoroacetic acid; inorganic acids such as hydrochloric acid and sulfuric acid; organic sulfonic acids such as paratoluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; organic phosphonic acids such as phosphoric acid; Heteropolyacids such as tungstosilicic acid, tungstophosphoric acid, molybdosilicic acid and molybdophosphoric acid; and the like can be used.
本発明の熱硬化性樹脂組成物において、さらに上記成分以外に、必要に応じて、充填材、シランカップリング剤、着色剤、難燃剤および離型剤など、公知の熱硬化性樹脂組成物に用いられる各種添加剤を用いることができる。 In the thermosetting resin composition of the present invention, in addition to the components described above, known thermosetting resin compositions such as a filler, a silane coupling agent, a colorant, a flame retardant, and a release agent may be used as necessary. The various additives used can be used.
本発明の熱硬化性樹脂組成物の製造方法としては、例えばノボラック型フェノール樹脂（ａ）、一般式（１）で表される構造を有する硬化剤(ｂ)、必要に応じて、上記硬化触媒及び各種添加剤を、公知のミキサーで混合することにより得ることができるが、これに限定されるものではない。また、これらの混合物を、加熱ロール及び二軸押し出し機などの混練機を用いて、溶融混合しても良い。 Examples of the method for producing the thermosetting resin composition of the present invention include a novolac type phenol resin (a), a curing agent (b) having a structure represented by the general formula (1), and, if necessary, the above curing catalyst. And various additives can be obtained by mixing with a known mixer, but are not limited thereto. Moreover, you may melt-mix these mixtures using kneading machines, such as a heating roll and a biaxial extruder.
本発明の成形材料に用いる充填材としては、有機充填材および無機充填材などの充填材を用いることができる。有機充填材としては、木粉、合板粉、熱硬化性樹脂硬化物粉末および粉砕布などが挙げられ、無機充填材としては、ガラスビーズ、ガラスパウダー、炭酸カルシウム、タルク、シリカ、水酸化アルミニウム、クレーおよびマイカなどの粉末状充填材や、ガラス繊維およびカーボン繊維などの繊維状充填材などが挙げられ、これらの１種以上が使用できるが、これらに限定されるものではない。 As the filler used in the molding material of the present invention, fillers such as organic fillers and inorganic fillers can be used. Examples of organic fillers include wood powder, plywood powder, thermosetting resin cured powder and crushed cloth, and inorganic fillers include glass beads, glass powder, calcium carbonate, talc, silica, aluminum hydroxide, Examples thereof include powdery fillers such as clay and mica, and fibrous fillers such as glass fiber and carbon fiber. One or more of these can be used, but are not limited thereto.
本発明の熱硬化性樹脂成形材料における充填材の含有量としては、前記熱硬化性樹脂組成物におけるノボラック型フェノール樹脂（ａ）及び前記一般式（１）で表される構造を有する硬化剤（ｂ）の合計量１００重量部に対して、好ましい下限値が３０重量部で、好ましい上限値が４００重量部である。前記数値の範囲外でも使用できるが、前記下限値以上であれば、本発明の熱硬化性樹脂成形材料の硬化物である成形品において、より十分な機械強度が得られ、前記上限値以下であれば、成形時の流動性もより良好であり、金型への充填性も良好である。 As content of the filler in the thermosetting resin molding material of this invention, the hardening | curing agent which has the structure represented by the novolak-type phenol resin (a) in the said thermosetting resin composition and the said General formula (1) ( A preferable lower limit is 30 parts by weight and a preferable upper limit is 400 parts by weight with respect to 100 parts by weight of the total amount of b). Although it can be used outside the range of the numerical value, if it is equal to or higher than the lower limit value, in the molded product that is a cured product of the thermosetting resin molding material of the present invention, more sufficient mechanical strength can be obtained, and less than the upper limit value. If it exists, the fluidity | liquidity at the time of shaping | molding is also more favorable, and the filling property to a metal mold | die is also favorable.
本発明の熱硬化性樹脂成形材料において、上記成分以外に、必要に応じて、シランカップリング剤、着色剤、難燃剤および離型剤など、公知の熱硬化性樹脂成形材料に用いられる各種添加剤を用いることができる。 In the thermosetting resin molding material of the present invention, in addition to the above components, various additions used for known thermosetting resin molding materials such as a silane coupling agent, a colorant, a flame retardant, and a release agent, as necessary. An agent can be used.
本発明の熱硬化性樹脂成形材料の製造方法としては、例えば、まず、前記熱硬化性樹脂組成物および充填材、必要に応じて、各種添加剤を、公知のミキサーにより混合して混合物を得る。次いで、この混合物を、加熱ロール及び二軸押し出し機などの混練機を用いて、溶融混合して得ることができるが、これに限定されない。 As a method for producing the thermosetting resin molding material of the present invention, for example, first, the thermosetting resin composition and the filler, and if necessary, various additives are mixed by a known mixer to obtain a mixture. . Next, the mixture can be obtained by melt mixing using a kneader such as a heating roll and a twin screw extruder, but is not limited thereto.
このようにして得られる本発明の熱硬化性樹脂組成物及び熱硬化性樹脂成形材料は、例えば、１５０〜２５０℃程度の温度で加熱することにより硬化物とすることができる。加熱温度及び加熱時間については、得られる硬化物の大きさや形状などに応じて、適宜設定して硬化させる。
また、上記成形材料とした場合、例えば、圧縮成形、移送成形及び射出成形などの成形方法により、加熱することにより成形して成形品とすることができる。
The thermosetting resin composition and the thermosetting resin molding material of the present invention thus obtained can be made into a cured product by heating at a temperature of about 150 to 250 ° C., for example. The heating temperature and the heating time are appropriately set and cured according to the size and shape of the obtained cured product.
Moreover, when it is set as the said molding material, it can shape | mold by heating by molding methods, such as compression molding, transfer molding, and injection molding, and can be made into a molded article.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によって何ら制約されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by these examples.
（合成例１）
容量１００ｍｌフラスコ中、１，２−ジクロロエタン（和光純薬工業（株）製）４５ｍｌに、２，６−ジ−ｔｅｒｔ−ブチルフェノール（関東化学（株）製）２０．６ｇ（１００ｍｍｏｌ）と４，４’−ビス（ブロモメチル）ビフェニル（東京化成工業（株）製）３．４ｇ（１０ｍｍｏｌ）と硫酸（和光純薬工業（株）製）０．５ｇを加え、１０時間還流しながら攪拌して反応させた。反応液を水洗したのち、反応液より２，６−ジ−ｔｅｒｔ−ブチルフェノールを１８０℃で減圧留去し、残渣を熱ヘキサン（和光純薬工業（株）製）を用いて、再結晶させた。これを濾過し、濾物を乾燥させた。濾物を乾燥後、トルエン（和光純薬工業（株）製）３００ｍｌに溶解させ、これに、三塩化アルミニウム（和光純薬工業（株）製）１.３ｇ（１０ｍｍｏｌ）を加え、室温で、５時間攪拌して反応させた。この反応液に水１００ｍｌを加えた後、水層を除去し、さらにトルエンを留去した後、残留物をジエチルエーテル（和光純薬工業（株）製）１００ｍｌに溶解し、パラホルムアルデヒド（住友商事（株））０.９ｇ（２８ｍｍｏｌ）、水１００ｍｌ及びカリウムブトキシド（東京化成工業（株）製）０.１６ｇ（１４ｍｍｏｌ）を加えて、４０℃で１０時間攪拌して、反応生成物を得た。これを塩酸（和光純薬工業（株）製）で中和し、溶媒を濾過して、ビフェノール型硬化剤（化合物Ａ）を得た。
(Synthesis Example 1)
In a 100 ml flask, 45 ml of 1,2-dichloroethane (manufactured by Wako Pure Chemical Industries, Ltd.), 20.6 g (100 mmol) of 2,6-di-tert-butylphenol (manufactured by Kanto Chemical Co., Ltd.) and 4,4 3.4 g (10 mmol) of '-bis (bromomethyl) biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.5 g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the reaction was stirred for 10 hours while refluxing. It was. After washing the reaction solution with water, 2,6-di-tert-butylphenol was distilled off from the reaction solution under reduced pressure at 180 ° C., and the residue was recrystallized using hot hexane (manufactured by Wako Pure Chemical Industries, Ltd.). . This was filtered and the filtrate was dried. The filtrate is dried and dissolved in 300 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.). To this, 1.3 g (10 mmol) of aluminum trichloride (manufactured by Wako Pure Chemical Industries, Ltd.) is added, and at room temperature, The reaction was stirred for 5 hours. After adding 100 ml of water to the reaction solution, the aqueous layer was removed, and toluene was distilled off. The residue was dissolved in 100 ml of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) and paraformaldehyde (Sumitomo Corporation). (Co)) 0.9 g (28 mmol), 100 ml of water and 0.16 g (14 mmol) of potassium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 40 ° C. for 10 hours to obtain a reaction product. . This was neutralized with hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent was filtered to obtain a biphenol type curing agent (Compound A).
（合成例２）
容量１００ｍｌフラスコ中、１，２−ジクロロエタン４５ｍｌに、パラ−ｔｅｒｔ−ブチルフェノール（関東化学（株）製）１５ｇ（1００ｍｍｏｌ）と２，６−ビス（ブロモメチル）ナフタレン（シグマアルドリッチ（株）製）３．１ｇ（１０ｍｍｏｌ）と硫酸（０．５ｇ）を加え、１０時間還流しながら攪拌して反応させた。反応液を水洗したのち、反応液よりパラ−ｔｅｒｔ−ブチルフェノールを１６０℃で減圧留去し、残渣を熱ヘキサンを用いて再結晶させた。これを濾過し、濾物を乾燥させた。濾物を乾燥後、トルエン３００ｍｌに溶解させ、これに、三塩化アルミニウム１.３ｇ（１０ｍｍｏｌ）を加え、室温で、５時間攪拌して反応させた。この反応液に水１００ｍｌを加えた後、水層を除去し、さらにトルエンを留去した後、残留物をジエチルエーテル１００ｍｌに溶解し、パラホルムアルデヒド０.９ｇ（２８ｍｍｏｌ）、水１００ｍｌ及びカリウムブトキシド０.１６ｇ（１４ｍｍｏｌ）を加えて、４０℃で１０時間攪拌して、反応生成物を得た。これを塩酸（和光純薬工業製）で中和し、溶媒を濾過して、オルトナフタレン型硬化剤（化合物Ｂ）を得た。
(Synthesis Example 2)
2. In a 100 ml flask, 45 g of 1,2-dichloroethane, 15 g (100 mmol) of para-tert-butylphenol (Kanto Chemical Co., Ltd.) and 2,6-bis (bromomethyl) naphthalene (Sigma Aldrich Co.) 1 g (10 mmol) and sulfuric acid (0.5 g) were added and reacted with stirring for 10 hours while refluxing. After the reaction solution was washed with water, para-tert-butylphenol was distilled off from the reaction solution under reduced pressure at 160 ° C., and the residue was recrystallized using hot hexane. This was filtered and the filtrate was dried. The filtrate was dried and dissolved in 300 ml of toluene. To this was added 1.3 g (10 mmol) of aluminum trichloride, and the mixture was stirred at room temperature for 5 hours to be reacted. 100 ml of water was added to the reaction solution, the aqueous layer was removed, and toluene was distilled off. The residue was dissolved in 100 ml of diethyl ether, and 0.9 g (28 mmol) of paraformaldehyde, 100 ml of water and potassium butoxide were added. .16 g (14 mmol) was added, and the mixture was stirred at 40 ° C. for 10 hours to obtain a reaction product. This was neutralized with hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent was filtered to obtain an orthonaphthalene type curing agent (Compound B).
（合成例３）
容量１００ｍｌフラスコ中、１，２−ジクロロエタン４５ｍｌに、２，６−ジ−ｔｅｒｔ−ブチルフェノール（関東化学（株）製）２０．６ｇ（1００ｍｍｏｌ）と２，６−ビス（ブロモメチル）ナフタレン（シグマアルドリッチ（株）製）３．１ｇ（１０ｍｍｏｌ）と硫酸（０．５ｇ）を加え、１０時間還流しながら攪拌して反応させた。反応液を水洗したのち、２，６−ジｔｅｒｔブチルフェノールを減圧留去し、残渣を熱ヘキサンを用いて再結晶させた。これを濾過し、濾物を乾燥させた。濾物を乾燥後、トルエン３００ｍｌに溶解させ、これに、三塩化アルミニウム１.３ｇ（１０ｍｍｏｌ）を加え、室温で、５時間攪拌して反応させた。この反応液に水１００ｍｌを加えた後、水層を除去し、トルエンを留去した後、残留物をジエチルエーテル１００ｍｌに溶解し、パラホルムアルデヒド0.９ｇ（２８ｍｍｏｌ）、水１００ｍｌ及びカリウムブトキシド０.１６ｇ（１４ｍｍｏｌ）を加えて、４０℃で１０時間攪拌して、反応生成物を得た。これを塩酸（和光純薬工業（株）製）で中和し、溶媒を濾過して、パラナフタレン型硬化剤（化合物Ｃ）を得た。
(Synthesis Example 3)
In a 100 ml flask, 45 ml of 1,2-dichloroethane was mixed with 20.6 g (100 mmol) of 2,6-di-tert-butylphenol (manufactured by Kanto Chemical Co., Ltd.) and 2,6-bis (bromomethyl) naphthalene (Sigma Aldrich ( 3.1 g (10 mmol) and sulfuric acid (0.5 g) were added, and the mixture was reacted with stirring for 10 hours while refluxing. After the reaction solution was washed with water, 2,6-ditertbutylphenol was distilled off under reduced pressure, and the residue was recrystallized using hot hexane. This was filtered and the filtrate was dried. The filtrate was dried and dissolved in 300 ml of toluene. To this was added 1.3 g (10 mmol) of aluminum trichloride, and the mixture was stirred at room temperature for 5 hours to be reacted. After adding 100 ml of water to this reaction solution, the aqueous layer was removed, and toluene was distilled off. The residue was dissolved in 100 ml of diethyl ether, 0.9 g (28 mmol) of paraformaldehyde, 100 ml of water, and 0.8% of potassium butoxide. 16 g (14 mmol) was added and stirred at 40 ° C. for 10 hours to obtain a reaction product. This was neutralized with hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent was filtered to obtain a paranaphthalene type curing agent (compound C).
（合成例４）
２，６−ジ−ｔｅｒｔ−ブチルフェノール２０．６ｇ（１００ｍｍｏｌ）を１００ｍｌのトルエンに溶解させ、さらに、ホルマリン（和光純薬工業（株）製）８.２ｇ(１００ｍｍｏｌ)を加えた。これらを１０℃まで冷却後、水酸化ナトリウム（和光純薬工業（株）製）４ｇ（１００ｍｍｏｌ）を水４ｇに溶解した水酸化ナトリウム水溶液を滴下した。これらを２４時間攪拌し、混合物を１５００ｍｌの水に投入後、酢酸で中和した。中和物中の沈殿物をろ過し、２，６−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシメチルフェノールを得た。得られた２，６−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシメチルフェノール１８．９ｇ（８０ｍｍｏｌ）に、アントラセン（東京化学工業（株）製）２９ｇ（１６０ｍｍｏｌ）、クロロベンゼン（和光純薬工業（株）製）８００ｍｌを加え、８０℃まで昇温させた。さらに２００ｍｌの塩酸を滴下し、８０℃で４８時間攪拌した。生成した沈殿物を濾過し、クロロベンゼンヘキサンと水で洗浄したのち、１００℃で減圧乾燥した。これに、トルエン２００ｍｌ、三塩化アルミニウム１０．６ｇ（４２ｍｍｏｌ）を加え、室温で、５時間攪拌して反応させた。この反応液に水１００ｍｌを加えた後、水層を除去し、さらにトルエンを留去した後、残留物をジエチルエーテル１００ｍｌに溶解し、パラホルムアルデヒド５．２ｇ（１６０ｍｍｏｌ）、水１００ｍｌ及びカリウムブトキシド８．９ｇ（８０ｍｍｏｌ）を加えて、４０℃で１０時間攪拌して、反応生成物を得た。これを塩酸（和光純薬工業（株）製）で中和し、溶媒を濾過して、アントラセン型硬化剤（化合物Ｄ）を得た。
(Synthesis Example 4)
20.6 g (100 mmol) of 2,6-di-tert-butylphenol was dissolved in 100 ml of toluene, and further 8.2 g (100 mmol) of formalin (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After cooling these to 10 ° C., an aqueous sodium hydroxide solution in which 4 g (100 mmol) of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 4 g of water was added dropwise. These were stirred for 24 hours, and the mixture was poured into 1500 ml of water and then neutralized with acetic acid. The precipitate in the neutralized product was filtered to obtain 2,6-di-tert-butyl-4-hydroxymethylphenol. To 18.9 g (80 mmol) of the obtained 2,6-di-tert-butyl-4-hydroxymethylphenol, 29 g (160 mmol) of anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), chlorobenzene (Wako Pure Chemical Industries, Ltd.) 800 ml) was added and the temperature was raised to 80 ° C. Further, 200 ml of hydrochloric acid was added dropwise and stirred at 80 ° C. for 48 hours. The produced precipitate was filtered, washed with chlorobenzene hexane and water, and then dried under reduced pressure at 100 ° C. To this, 200 ml of toluene and 10.6 g (42 mmol) of aluminum trichloride were added, and the reaction was allowed to stir at room temperature for 5 hours. 100 ml of water was added to the reaction solution, the aqueous layer was removed, and toluene was further distilled off. The residue was dissolved in 100 ml of diethyl ether, and 5.2 g (160 mmol) of paraformaldehyde, 100 ml of water and potassium butoxide 8 .9 g (80 mmol) was added and stirred at 40 ° C. for 10 hours to obtain a reaction product. This was neutralized with hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the solvent was filtered to obtain an anthracene type curing agent (Compound D).
（実施例１）
数平均分子量９００、融点９２℃のノボラック型フェノール・ホルムアルデヒド樹脂８７重量部、合成例１で得た化合物Ａ１２１重量部を、常温で乳鉢を用い混合し、熱硬化性樹脂組成物を得た。
上記で得られた熱硬化性樹脂組成物を用いて、１５０℃の熱板上で３分間攪拌した後、上記樹脂組成物１１ｇを金型に入れ、９．８ＭＰａで加圧し、１５０℃で５分間加熱して硬化させ、１００ｘ１０ｘ４ｍｍの成形品を作製し、これを、１７５℃６時間ポストキュアした。得られた成形品を５０ｘ４ｘ３ｍｍに切断し、セイコーインスツルメンツ製ＤＭＳ６１００により曲げモードで１０Ｈｚ，５℃/分で昇温させてｔａｎδのピークトップをガラス移転移転点Ｔｇとし、貯蔵弾性率Ｅ'とともに測定した。
Example 1
87 parts by weight of a novolac type phenol / formaldehyde resin having a number average molecular weight of 900 and a melting point of 92 ° C. and 121 parts by weight of the compound A obtained in Synthesis Example 1 were mixed at room temperature using a mortar to obtain a thermosetting resin composition.
After stirring for 3 minutes on a hot plate at 150 ° C. using the thermosetting resin composition obtained above, 11 g of the resin composition was placed in a mold, pressurized at 9.8 MPa, and 5 ° C. at 150 ° C. It was cured by heating for 100 minutes to produce a molded product of 100 × 10 × 4 mm, which was post-cured at 175 ° C. for 6 hours. The obtained molded product was cut into 50 × 4 × 3 mm, and heated at 10 Hz, 5 ° C./min in a bending mode with a DMS6100 manufactured by Seiko Instruments Inc., and the peak top of tan δ was set as the glass transfer transfer point Tg and measured together with the storage elastic modulus E ′. .
（実施例２〜６）
実施例１において、化合物Ａ１２１重量部を、化合物Ａ〜Ｄにそれぞれ表１のように配合した以外は実施例１と同様にして、樹脂組成物と硬化物（成形品）を得た。得られた硬化物の測定結果を表１に示した。
(Examples 2 to 6)
In Example 1, a resin composition and a cured product (molded article) were obtained in the same manner as in Example 1 except that 121 parts by weight of Compound A was added to each of Compounds A to D as shown in Table 1. The measurement results of the obtained cured product are shown in Table 1.
（比較例１）
まず、特開平６−１８４４０５号公報の製造例に準じて数平均分子量７５０、融点７５℃のジメチレンエーテル型フェノール樹脂を合成した。
数平均分子量９００、融点９２℃のノボラック型フェノール樹脂３０重量部と、化合物Ａの代わりに上記で得た数平均分子量７５０、融点７５℃のジメチレンエーテル型フェノール樹脂６０重量部、及び数平均分子量４５０、融点８５℃のメチロール型フェノール樹脂１０重量部とを用い、実施例１と同様の操作により、樹脂組成物と硬化物（成形品）を得た。得られた硬化物の測定結果を表１に示した。
(Comparative Example 1)
First, a dimethylene ether type phenol resin having a number average molecular weight of 750 and a melting point of 75 ° C. was synthesized according to the production example of JP-A-6-184405.
Number average molecular weight 900, melting point 92 ° C. novolac type phenol resin 30 parts by weight, instead of compound A, number average molecular weight 750 obtained above, melting point 75 ° C. dimethylene ether type phenol resin 60 parts by weight, and number average molecular weight A resin composition and a cured product (molded product) were obtained in the same manner as in Example 1 using 450 parts by weight and 10 parts by weight of a methylol phenol resin having a melting point of 85 ° C. The measurement results of the obtained cured product are shown in Table 1.
（実施例７〜１０及び比較例２）
表２に示す割合で、熱硬化性樹脂組成物、充填材及び添加剤を配合した原料を、加熱ロールで混練し、更に混練物を冷却、粉砕して、それぞれ、成形材料を得た。得られた成形材料を用いて、実施例１と同様にして、Ｔｇ及びＥ’を測定するとともに、硬化速度の指標であるバコール硬度の測定を行い、測定結果を表２に示した。
バコール硬度は、１７５℃に設定した移送成形用金型に、圧力２０ＭＰａで注入して、５０ｍｍφ＊３ｍｍ厚みの成形品を成形して得られた成形品を、バコール硬度計（Ｎｏ．９３５）により硬度測定を行い、成形品のバコール硬度が４０以上になった時の硬化時間で表す。この時間が短いほど、硬化速度が速いことを示す。
(Examples 7 to 10 and Comparative Example 2)
The raw materials blended with the thermosetting resin composition, the filler and the additive at the ratio shown in Table 2 were kneaded with a heating roll, and the kneaded product was cooled and pulverized to obtain molding materials, respectively. Using the obtained molding material, Tg and E ′ were measured in the same manner as in Example 1, and the Bacol hardness, which is an index of the curing rate, was measured. The measurement results are shown in Table 2.
The Bacol hardness is injected into a transfer mold set at 175 ° C. at a pressure of 20 MPa, and a molded product obtained by molding a molded product having a thickness of 50 mmφ * 3 mm is obtained by a Bacol hardness meter (No. 935). The hardness is measured, and it is represented by the curing time when the Bacol hardness of the molded product is 40 or more. The shorter this time, the faster the curing rate.
上記の表１及び表２の結果から明らかな様に、本発明の熱硬化性樹脂組成物及び熱硬化性樹脂成形材料は、高い耐熱性と強度を有する。 As is apparent from the results of Tables 1 and 2, the thermosetting resin composition and the thermosetting resin molding material of the present invention have high heat resistance and strength.
本発明の硬化性樹脂組成物は、硬化物として優れた耐熱性を有することから、従来より、熱硬化性フェノール樹脂組成物が用いられてきた積層板及び接着剤等の用途や、同様に熱硬化性樹脂成形材料が用いられている自動車用部品、機構部品及び電機・電子部品等の用途に好適である。 Since the curable resin composition of the present invention has excellent heat resistance as a cured product, it has been conventionally used for laminates and adhesives for which thermosetting phenol resin compositions have been used, as well as heat. It is suitable for applications such as automotive parts, mechanical parts, and electric / electronic parts in which a curable resin molding material is used.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011195515A (en) * | 2010-03-19 | 2011-10-06 | Asahi Organic Chemicals Industry Co Ltd | Anthracene derivative, resin, curable composition, and cured product |
| JP2012087103A (en) * | 2010-10-21 | 2012-05-10 | Asahi Organic Chemicals Industry Co Ltd | Anthracene derivative, curable composition, and cured product |
| JP2016155930A (en) * | 2015-02-24 | 2016-09-01 | 群栄化学工業株式会社 | Phenol resol resin |
| JP2019172717A (en) * | 2018-03-26 | 2019-10-10 | 味の素株式会社 | Resin composition |
-
2008
- 2008-05-29 JP JP2008140551A patent/JP2009286888A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011195515A (en) * | 2010-03-19 | 2011-10-06 | Asahi Organic Chemicals Industry Co Ltd | Anthracene derivative, resin, curable composition, and cured product |
| JP2012087103A (en) * | 2010-10-21 | 2012-05-10 | Asahi Organic Chemicals Industry Co Ltd | Anthracene derivative, curable composition, and cured product |
| JP2016155930A (en) * | 2015-02-24 | 2016-09-01 | 群栄化学工業株式会社 | Phenol resol resin |
| JP2019172717A (en) * | 2018-03-26 | 2019-10-10 | 味の素株式会社 | Resin composition |
| JP7163605B2 (en) | 2018-03-26 | 2022-11-01 | 味の素株式会社 | resin composition |
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