JP5918425B1 - Imido group-containing naphthol resin production method, thermosetting resin composition, cured product thereof, and use - Google Patents

Imido group-containing naphthol resin production method, thermosetting resin composition, cured product thereof, and use Download PDF

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JP5918425B1
JP5918425B1 JP2015125997A JP2015125997A JP5918425B1 JP 5918425 B1 JP5918425 B1 JP 5918425B1 JP 2015125997 A JP2015125997 A JP 2015125997A JP 2015125997 A JP2015125997 A JP 2015125997A JP 5918425 B1 JP5918425 B1 JP 5918425B1
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naphthol
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真司 恩田
真司 恩田
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Abstract

【課題】機械的特性が良好であって、成形物の自由度が高い樹脂原料として有用なイミド基含有ナフトール樹脂の製造方法、熱硬化性樹脂組成物およびその硬化物ならびに用途を提供すること。【解決手段】ナフトール化合物をビスマレイミド化合物で連結するナフトール化ステップによって、ビスマレイミド化合物がナフトール化合物の連結に用いられてナフトール化合物になっているから、後に熱硬化性樹脂を硬化させる際にビスマレイミド化合物同士が重合反応することを防いで、硬化物が脆くなることがなく、機械的特性の良好な成形物を得ることができる。【選択図】 なしAn object of the present invention is to provide a method for producing an imide group-containing naphthol resin useful as a resin raw material having good mechanical properties and a high degree of freedom in a molded product, a thermosetting resin composition, a cured product thereof, and an application. According to a naphtholization step in which a naphthol compound is linked with a bismaleimide compound, the bismaleimide compound is used to link the naphthol compound to form a naphthol compound, so that the bismaleimide is subsequently cured when the thermosetting resin is cured. It is possible to prevent a compound from reacting with each other and to obtain a molded article having good mechanical properties without the cured product becoming brittle. [Selection figure] None

Description

本発明は、引張弾性率、引張強度、伸び率などの機械的特性に優れる耐熱性樹脂の原料として有用なイミド基含有ナフトール樹脂製造方法、熱硬化性樹脂組成物およびその硬化物ならびに用途に関する。   The present invention relates to a method for producing an imide group-containing naphthol resin, a thermosetting resin composition useful as a raw material for a heat-resistant resin having excellent mechanical properties such as tensile elastic modulus, tensile strength, and elongation, a cured product thereof, and an application.

電気電子産業を中心に各種の分野において、絶縁材料、接着剤、フィルム原料用樹脂などに使用できる樹脂材料が求められている。これら用途の樹脂材料に要求される性質を備えた樹脂材料として、特許文献１には変性ポリイミド樹脂組成物が開示されている。当該変性ポリイミド樹脂組成物は、高い耐熱性、機械的強度、誘電特性と同時に、吸湿性、接着性を実現することを目的としており、（ａ）ポリマレイミド化合物と（ｂ）分子中に少なくとも二つ以上のＯＨ基および少なくとも一つのナフタレン骨格を有するフェノール樹脂と（ｃ）分子中に少なくとも二つ以上のグリシジル基を有する樹脂とを所定割合で含有してなる。   Resin materials that can be used as insulating materials, adhesives, resins for film raw materials, and the like have been demanded in various fields mainly in the electric and electronic industries. Patent Document 1 discloses a modified polyimide resin composition as a resin material having properties required for resin materials for these uses. The modified polyimide resin composition is intended to achieve high heat resistance, mechanical strength, and dielectric properties as well as hygroscopicity and adhesiveness, and includes (a) a polymaleimide compound and (b) at least two molecules in the molecule. A phenol resin having at least one OH group and at least one naphthalene skeleton and (c) a resin having at least two glycidyl groups in the molecule are contained in a predetermined ratio.

特開２００３−７３４５９号公報JP 2003-73459 A

しかし、特許文献１に開示された変性ポリイミド樹脂組成物は、引張弾性率、引張強度、伸び率などの機械的特性が十分ではない。このため、変性ポリイミド樹脂組成物を用いて機械的特性が良好な成形物を得るためには、基材を併用する必要があり、その硬化物のみから機械的特性の良好な成形物を得ることができないという問題があった。   However, the modified polyimide resin composition disclosed in Patent Document 1 does not have sufficient mechanical properties such as tensile elastic modulus, tensile strength, and elongation. For this reason, in order to obtain a molded product with good mechanical properties using the modified polyimide resin composition, it is necessary to use a base material together, and to obtain a molded product with good mechanical properties only from the cured product. There was a problem that could not.

そこで、本発明は、機械的特性が良好であって、基材を併用しなくても機械的特性の良好な成形物を得ることができる成形物の自由度が高い樹脂原料として有用なイミド基含有ナフトール樹脂の製造方法、熱硬化性樹脂組成物およびその硬化物ならびに用途の提供を目的とする。   Therefore, the present invention provides an imide group useful as a resin raw material having high mechanical properties and having a high degree of freedom of a molded product that can obtain a molded product having good mechanical properties without using a base material in combination. It aims at provision of the manufacturing method of a containing naphthol resin, a thermosetting resin composition, its hardened | cured material, and a use.

上記の課題を解決するために提供される本発明は次のとおりである。
（１）ナフトール化合物の水酸基１当量に対して、ビスマレイミド化合物のマレイミド基０．１０〜０．４０当量を反応させて前記ナフトール化合物を前記ビスマレイミド化合物で連結するナフトール化ステップを備えているイミド基含有ナフトール樹脂の製造方法。
（２）前記ナフトール化合物は、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有する（１）に記載のイミド基含有ナフトール樹脂の製造方法。
（３）前記ビスマレイミド化合物は、エーテル結合および四つの芳香族環を有する（１）または（２）に記載のイミド基含有ナフトール樹脂の製造方法。
（４）前記ナフトール化ステップは、前記ナフトール化合物と前記ビスマレイミド化合物とを溶媒中で加熱するステップである請求項（１）〜（３）のいずれか一つに記載のイミド基含有ナフトール樹脂の製造方法。 The present invention provided to solve the above-described problems is as follows.
(1) imide on 1 equivalent of hydroxyl group of the naphthol compound, a naphthol of steps for connecting the naphthol compound the bis-maleimide compound is reacted maleimide groups 0.10 to 0.40 equivalents of bis-maleimide compound A method for producing a group-containing naphthol resin.
(2) The method for producing an imide group-containing naphthol resin according to (1), wherein the naphthol compound has two or more hydroxy groups and one or two or more naphthalene skeletons in a molecule.
(3) The method for producing an imide group-containing naphthol resin according to (1) or (2), wherein the bismaleimide compound has an ether bond and four aromatic rings.
(4) The naphtholization step is a step of heating the naphthol compound and the bismaleimide compound in a solvent. The imide group-containing naphthol resin according to any one of claims (1) to (3), Production method.

（５）ナフトール化合物の水酸基１当量に対して、ビスマレイミド化合物のマレイミド基０．１０〜０．４０当量を反応させて前記ナフトール化合物を前記ビスマレイミド化合物で連結するナフトール化ステップを備えている、イミド基含有ナフトール樹脂を含有する熱硬化性樹脂硬化剤の製造方法。
（６）水酸基当量が２５０〜６００ｇ／ｅｑである、（５）に記載の熱硬化性樹脂硬化剤の製造方法。
(5) relative to 1 equivalent of hydroxyl group of the naphthol compound, a naphthol of steps for connecting the naphthol compound the bis-maleimide compound is reacted maleimide groups 0.10 to 0.40 equivalents of bis-maleimide compound, A method for producing a thermosetting resin curing agent containing an imide group-containing naphthol resin.
(6) The method for producing a thermosetting resin curing agent according to (5), wherein the hydroxyl group equivalent is 250 to 600 g / eq.

（７）ビスマレイミド化合物とナフトール化合物とを含んでおり、ナフトール化合物の水酸基１当量に対して、前記ビスマレイミド化合物のマレイミド基が０．１０〜０．４０当量であり、前記ビスマレイミド化合物が、エーテル結合および四つの芳香族環を有しており、前記ナフトール化合物が、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有している樹脂組成物。
（８）さらに分子中に二つ以上のグリシジル基を有するエポキシ樹脂を含んでおり、前記ナフトール化合物の水酸基１当量に対して、前記マレイミド化合物のマレイミド基当量と前記エポキシ樹脂のエポキシ基当量との合計が０．８〜１．５当量である（７）に記載の樹脂組成物。
 (7) A bismaleimide compound and a naphthol compound are included, and the maleimide group of the bismaleimide compound is 0.10 to 0.40 equivalent with respect to 1 equivalent of the hydroxyl group of the naphthol compound, and the bismaleimide compound is A resin composition having an ether bond and four aromatic rings, wherein the naphthol compound has two or more hydroxy groups and one or two or more naphthalene skeletons in a molecule.
(8) Furthermore, the epoxy resin which has two or more glycidyl groups in a molecule | numerator is included, The maleimide group equivalent of the said maleimide compound and the epoxy group equivalent of the said epoxy resin are equivalent with respect to 1 equivalent of hydroxyl groups of the said naphthol compound. The resin composition as described in (7) whose sum total is 0.8-1.5 equivalent.

（９）（７）または（８）に記載の熱硬化性樹脂硬化剤を含有している熱硬化性樹脂組成物。
（１０）さらに硬化促進剤を含む（９）に記載の熱硬化性樹脂組成物。
（１１）さらに無機充填材を含む（９）または（１０）に記載の熱硬化性樹脂組成物。 (9) A thermosetting resin composition containing the thermosetting resin curing agent according to (7) or (8).
(10) The thermosetting resin composition according to (9) , further including a curing accelerator.
(11) The thermosetting resin composition according to (9) or (10) , further including an inorganic filler.

（１２）（９）〜（１１）のいずれか一つに記載の熱硬化性樹脂組成物を硬化させた硬化物。 (12) A cured product obtained by curing the thermosetting resin composition according to any one of (9) to (11) .

（１３）（９）〜（１１）のいずれか一つに記載の熱硬化性樹脂組成物からなる層間絶縁材料。 (13) An interlayer insulating material comprising the thermosetting resin composition according to any one of (9) to (11) .

（１４）（９）〜（１１）のいずれか一つに記載の熱硬化性樹脂を、繊維状補強材に含浸させ加熱乾燥し、半硬化させて得られたプリプレグ。 (14) A prepreg obtained by impregnating a fibrous reinforcing material with the thermosetting resin according to any one of (9) to (11) , drying by heating, and semi-curing.

本発明により、各種の分野において用いられる、誘電特性および機械的特性の良好な硬化物の樹脂原料として有用な、イミド基含有ナフトール樹脂の製造方法、熱硬化性樹脂組成物、およびその硬化物ならびに用途が提供される。   INDUSTRIAL APPLICABILITY According to the present invention, a method for producing an imide group-containing naphthol resin, a thermosetting resin composition, and a cured product thereof, useful as a resin raw material for cured products having good dielectric properties and mechanical properties used in various fields. Applications are provided.

ビスマレイミド化合物類は、耐熱性樹脂の原料として広く用いられている。例えば、特許文献１（特開２００３−７３４５９号公報）にはビスマレイミド化合物、特定のフェノール樹脂、およびエポキシ樹脂を加熱混合した変性ポリイミド樹脂組成物が記載されている。この変性ポリイミド樹脂組成物を硬化した硬化物により耐熱性の成形物が得られる。   Bismaleimide compounds are widely used as raw materials for heat-resistant resins. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-73459) describes a modified polyimide resin composition obtained by heating and mixing a bismaleimide compound, a specific phenol resin, and an epoxy resin. A heat-resistant molded product is obtained from a cured product obtained by curing the modified polyimide resin composition.

しかし、上記変性ポリイミド樹脂組成物の硬化物は脆く、引張弾性率、引張強度、伸び率などの機械的特性が十分ではない。このため、上記変性ポリイミド樹脂組成物は、ガラスクロスなどの基材に含浸などさせた状態で硬化され、基材の機械的特性が付加された成形物として用いる必要があった。そこで、基材を併用しなくても硬化物それ自体として良好な機械的特性を備えた、成形物としての自由度が高い耐熱性樹脂原料が望まれている。   However, the cured product of the modified polyimide resin composition is brittle and has insufficient mechanical properties such as tensile modulus, tensile strength, and elongation. For this reason, the modified polyimide resin composition is required to be used as a molded product which is cured in a state where it is impregnated into a substrate such as a glass cloth and has the mechanical properties of the substrate added thereto. Therefore, there is a demand for a heat-resistant resin material having a high degree of freedom as a molded product, which has good mechanical properties as a cured product itself without using a substrate.

発明者は、イミド基含有ナフトール樹脂の硬化物が脆くなる原因を検討した結果、硬化の際にビスマレイミド化合物間で重合反応が生じることが硬化物の機械的特性低下の一因であることを見出した。そして、このビスマレイミド化合物同士の重合反応を抑制すること、および特定のビスマレイミド化合物を用いて重合反応の影響を抑制することにより、硬化物の誘電特性を良好に維持したまま、引張強度、伸び率、伸び率などの機械的特性が大幅に向上した硬化物が得られることを見出した。本発明は、この新たな知見にもとづいたものである。   As a result of examining the reason why the cured product of the imide group-containing naphthol resin becomes brittle, the inventor has found that a polymerization reaction between the bismaleimide compounds during curing is a cause of a decrease in mechanical properties of the cured product. I found it. Then, by suppressing the polymerization reaction between the bismaleimide compounds, and by suppressing the influence of the polymerization reaction using a specific bismaleimide compound, the tensile strength, the elongation, and the dielectric properties of the cured product are maintained well. It has been found that a cured product having significantly improved mechanical properties such as rate and elongation can be obtained. The present invention is based on this new knowledge.

（実施の形態１）
本実施の形態では、ビスマレイミド化合物同士の重合反応を抑制することによって、硬化物の機械的特性が大幅に向上するという知見にもとづいて本発明を実施する形態について説明する。
本実施の形態のイミド基含有ナフトール樹脂の製造方法は、ナフトール化合物をビスマレイミド化合物で連結するナフトール化ステップを備えている。本実施の形態の製造方法により製造されたイミド基含有ナフトール樹脂は、ナフトール化ステップによって、ビスマレイミド化合物のマレイミド基がスクシンイミドになり、得られるイミド基含有ナフトール樹脂にはマレイミド基が残存していない。このため、イミド基含有ナフトール樹脂を硬化剤として用いて熱硬化性樹脂を硬化させる際、ビスマレイミド化合物同士の重合反応が起こらない。すなわち、ビスマレイミド化合物は、予めナフトール化合物を連結するために用いられてナフトール化合物になっているから、後に熱硬化性樹脂を硬化させる際にビスマレイミド化合物同士が重合反応することがない。
したがって、ナフトール化ステップを経たイミド基含有ナフトール樹脂を用いることにより、誘電特性を低下させることなく、引張弾性率、引張強度や伸び率などの機械的特性が大幅に向上した熱硬化性樹脂の硬化物を得ることができる。 (Embodiment 1)
In the present embodiment, an embodiment for carrying out the present invention will be described based on the knowledge that the mechanical properties of a cured product are greatly improved by suppressing the polymerization reaction between bismaleimide compounds.
The manufacturing method of the imide group containing naphthol resin of this Embodiment is equipped with the naphtholation step which connects a naphthol compound with a bismaleimide compound. In the imide group-containing naphthol resin produced by the production method of the present embodiment, the maleimide group of the bismaleimide compound becomes succinimide by the naphtholation step, and no maleimide group remains in the obtained imide group-containing naphthol resin. . For this reason, when hardening thermosetting resin using an imide group containing naphthol resin as a hardening | curing agent, the polymerization reaction of bismaleimide compounds does not occur. That is, since the bismaleimide compound is used in advance to connect the naphthol compounds to form a naphthol compound, the bismaleimide compounds do not undergo a polymerization reaction when the thermosetting resin is cured later.
Therefore, by using an imide group-containing naphthol resin that has undergone a naphtholization step, curing of thermosetting resins with significantly improved mechanical properties such as tensile modulus, tensile strength, and elongation without reducing dielectric properties You can get things.

本実施の形態において「ナフトール化合物をビスマレイミド化合物で連結する」とは、ビスマレイミド化合物とナフトール化合物とを反応させて、ビスマレイミドの両端にナフトール化合物を連結することをいう。「ナフトール化合物をビスマレイミド化合物で連結」して得られたイミド基含有ナフトール樹脂からはビスマレイミド化合物が検出されない。ビスマレイミド化合物が検出されないとは、ゲル浸透クロマトグラフィー（Gel Permeation Chromatography：GPC）を用いて評価した場合に、ビスマレイミド化合物のピークが完全に消失していることをいう。   In the present embodiment, “connecting a naphthol compound with a bismaleimide compound” means reacting a bismaleimide compound and a naphthol compound to connect a naphthol compound to both ends of the bismaleimide. The bismaleimide compound is not detected from the imide group-containing naphthol resin obtained by “linking the naphthol compound with the bismaleimide compound”. The fact that the bismaleimide compound is not detected means that the peak of the bismaleimide compound has completely disappeared when evaluated using gel permeation chromatography (GPC).

ナフトール化ステップで用いられるナフトール化合物として、ナフトールアラルキル樹脂、ナフトールビフェニルアラルキル樹脂などが挙げられる。これらナフトール化合物のうち、硬化物の誘電特性を良好に維持したまま機械的特性を向上させる観点から、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有するナフトール化合物が好ましく用いられる。上記構造を備えた市販のナフトール化合物（樹脂）としては、例えば、ナフトールアラルキル樹脂、ＳＮ−４７５、ＳＮ−４８５、ＳＮ−４９５（商品名、新日鉄住金化学（株）社製）などが挙げられる。   Examples of naphthol compounds used in the naphtholization step include naphthol aralkyl resins and naphthol biphenyl aralkyl resins. Among these naphthol compounds, naphthol compounds having two or more hydroxy groups and one or two or more naphthalene skeletons in the molecule from the viewpoint of improving the mechanical properties while maintaining the dielectric properties of the cured product well. Is preferably used. Examples of commercially available naphthol compounds (resins) having the above structure include naphthol aralkyl resins, SN-475, SN-485, and SN-495 (trade names, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

ナフトール化ステップで用いられるビスマレイミド化合物として、ビス（４−マレイミドフェニル）メタン、ビス（４−マレイミドフェニル）エーテル、ビス（４−マレイミドフェニル）スルホン、３，３−ジメチル−５，５−ジエチル−４，４−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、ｍ−フェニレンビスマレイミド、２，２−ビス（４−（４−マレイミドフェノキシ）フェニル）プロパンなどが挙げられる。これらビスマレイミド化合物のうち、硬化物の誘電特性を良好に維持したまま機械的特性を向上させる観点から、熱硬化性樹脂との相溶性が良好な、エーテル結合および四つの芳香族環を有するビスマレイミド化合物が好ましく用いられる。このような構造を有するビスマレイミド化合物としては、２，２’−ビス−［４−（４−マレイミドフェノキシ）フェニル］プロパンが挙げられる。上記構造を備えた市販品としては、ＢＭＩ−４０００（商品名、大和化成工業（株）社製）、ＢＭＩ−８０（商品名、ケイアイ化成（株）社製）が挙げられる。   As bismaleimide compounds used in the naphtholation step, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl- Examples include 4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, and the like. Among these bismaleimide compounds, from the viewpoint of improving the mechanical properties while maintaining the dielectric properties of the cured product in good condition, the bis-maleimide compound is a bis having an ether bond and four aromatic rings with good compatibility with the thermosetting resin. Maleimide compounds are preferably used. Examples of the bismaleimide compound having such a structure include 2,2'-bis- [4- (4-maleimidophenoxy) phenyl] propane. Examples of commercially available products having the above structure include BMI-4000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and BMI-80 (trade name, manufactured by KAI Kasei Co., Ltd.).

ナフトール化ステップでは、ナフトール化合物とビスマレイミド化合物とを溶解した溶液を加熱することによって、ナフトール化合物をビスマレイミド基で連結する。このときの温度は、マレイミド基同士の重合反応を抑制するという観点から、８０〜１８０℃であることが好ましく、１００〜１６０℃であることがより好ましく、１２０〜１５０℃であることがさらに好ましい。   In the naphtholation step, the naphthol compound is linked with a bismaleimide group by heating a solution in which the naphthol compound and the bismaleimide compound are dissolved. The temperature at this time is preferably 80 to 180 ° C., more preferably 100 to 160 ° C., and further preferably 120 to 150 ° C., from the viewpoint of suppressing the polymerization reaction between maleimide groups. .

ナフトール化ステップにおいて用いられる、ビスマレイミド化合物とナフトール化合物との配合量は、ビスマレイミド化合物に対してナフトール化合物が過剰となるようにする。これにより、ナフトール化ステップにおいて、ビスマレイミド化合物のすべてがナフトール化合物の連結に用いられ、得られたイミド基含有ナフトール樹脂からビスマレイミド化合物が検出されなくなる。したがって、後にエポキシ樹脂などの硬化反応においてビスマレイミド化合物同士が反応して硬化物の機械的特性が低下することを防止できる。   The blending amount of the bismaleimide compound and the naphthol compound used in the naphtholization step is such that the naphthol compound is excessive with respect to the bismaleimide compound. Thereby, in the naphtholation step, all of the bismaleimide compound is used for linking the naphthol compound, and the bismaleimide compound is not detected from the obtained imide group-containing naphthol resin. Therefore, it is possible to prevent the bismaleimide compounds from reacting with each other later in the curing reaction of an epoxy resin or the like, thereby reducing the mechanical properties of the cured product.

マレイミド化合物の配合量は、得られたイミド基含有ナフトール樹脂からビスマレイミド化合物が検出されなくするという観点から、ナフトール化合物の水酸基１当量に対して、マレイミド基が０．１０〜０．４０当量であることが好ましく、マレイミド基が０．１５〜０．３５当量であることがより好ましく、マレイミド基が０．２０〜０．３０当量であることがさらに好ましい。   From the viewpoint of preventing the bismaleimide compound from being detected from the imide group-containing naphthol resin, the maleimide compound is blended in an amount of 0.10 to 0.40 equivalents of maleimide group to 1 equivalent of hydroxyl group of the naphthol compound. It is preferable that the maleimide group is 0.15 to 0.35 equivalent, and the maleimide group is more preferably 0.20 to 0.30 equivalent.

上述したとおり、ビスマレイミド化合物に対するナフトール化合物が過剰であるか否かは、水酸基当量とマレイミド基当量とを比較して判断する。ただし、特定の構造を有するビスマレイミド化合物とナフトール化合物であれば、両者の好ましい配合比を質量で特定することができる。
例えば、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有するナフトール化合物を、エーテル結合および四つの芳香族環を有しているビスマレイミド化合物で連結する場合、ビスマレイミド化合物１００質量部に対して用いられるナフトール化合物は２００〜１０００質量部であることが好ましく、２５０〜８００質量部であることがより好ましく、３００〜６００質量部であることがさらに好ましい。 As described above, whether or not the naphthol compound is excessive with respect to the bismaleimide compound is determined by comparing the hydroxyl group equivalent and the maleimide group equivalent. However, if it is a bismaleimide compound and a naphthol compound which have a specific structure, the preferable compounding ratio of both can be specified by mass.
For example, when a naphthol compound having two or more hydroxy groups and one or two or more naphthalene skeletons in a molecule is connected with a bismaleimide compound having an ether bond and four aromatic rings, The naphthol compound used for 100 parts by mass of the maleimide compound is preferably 200 to 1000 parts by mass, more preferably 250 to 800 parts by mass, and even more preferably 300 to 600 parts by mass.

ナフトール化ステップにおいて用いられる溶媒は、１２０℃以上の温度にすることができ、ビスマレイミド化合物およびナフトール化合物の溶解性が良好なものを用いる。このような性質を備えた溶媒として、例えば、プロピレングリコールモノメチルエーテル、シクロヘキサノン、シクロペンタノン、ジグライム、トリグライム、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、γ−ブチロラクトン、プロピレングリコール１−モノメチルエーテル２−アセタート（ＰＧＭＥＡ）などが挙げられる。   The solvent used in the naphtholization step can be a temperature of 120 ° C. or higher, and a solvent having good solubility of the bismaleimide compound and the naphthol compound is used. Examples of the solvent having such properties include propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, diglyme, triglyme, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N-methyl. -2-pyrrolidone (NMP), γ-butyrolactone, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and the like.

以上説明したように、本実施の形態のイミド基含有ナフトール樹脂の製造方法によれば、ナフトール化ステップによって、ビスマレイミド化合物をナフトール化合物としたイミド基含有ナフトール樹脂が得られる。したがって、イミド基含有ナフトール樹脂を熱硬化性樹脂硬化剤として用いた熱硬化反応の際、ビスマレイミド化合物同士の重合反応が生じない。これにより、誘電特性が良好であって、引張弾性率、引張強度、伸び率などの機械的特性が従来よりも大幅に向上した硬化物であって、基材と併用しなくても、硬化物単独でシート状などの成形物として用いることができる熱硬化性樹脂硬化剤が得られる。   As described above, according to the method for producing an imide group-containing naphthol resin of the present embodiment, an imide group-containing naphthol resin in which a bismaleimide compound is used as a naphthol compound is obtained by a naphtholization step. Therefore, the polymerization reaction between the bismaleimide compounds does not occur during the thermosetting reaction using the imide group-containing naphthol resin as the thermosetting resin curing agent. As a result, the cured product has good dielectric properties and mechanical properties such as tensile elastic modulus, tensile strength, and elongation that are significantly improved compared to conventional products. A thermosetting resin curing agent that can be used alone as a sheet-like molded product is obtained.

本実施の形態のイミド基含有ナフトール樹脂は、エポキシ樹脂などの熱硬化性樹脂の熱硬化用の熱硬化性樹脂硬化剤として用いることができる。熱硬化性樹脂硬化剤は、その一部としてイミド基含有ナフトール樹脂を含むもの、およびその全部がイミド基含有ナフトール樹脂であるもののいずれも含む。   The imide group-containing naphthol resin of the present embodiment can be used as a thermosetting resin curing agent for thermosetting a thermosetting resin such as an epoxy resin. The thermosetting resin curing agent includes both those containing an imide group-containing naphthol resin as a part thereof and those all of which are imide group-containing naphthol resins.

本実施の形態のイミド基含有ナフトール樹脂は、硬化物の機械的特性が良好になるという観点から、下記の一般式（１）表されるものが好ましい。
（一般式（１）において、ｌおよびｍは１〜１０、ｎは０〜３の整数）
上記一般式（１）で示されるイミド基含有ナフトール樹脂は、ナフトール化合物がビスマレイミド化合物により連結されている。このため、硬化性樹脂を硬化させる際に、ビスマレイミド化合物同士の重合反応が生じない。したがって硬化物が脆くなることがなく、成形物の形状および用途の自由度が高い、機械的特性が良好な硬化物が得られる。 The imide group-containing naphthol resin of the present embodiment is preferably represented by the following general formula (1) from the viewpoint of improving the mechanical properties of the cured product.
(In the general formula (1), l and m are 1 to 10 and n is an integer of 0 to 3)
In the imide group-containing naphthol resin represented by the general formula (1), the naphthol compound is linked by a bismaleimide compound. For this reason, when hardening curable resin, the polymerization reaction of bismaleimide compounds does not arise. Therefore, the cured product does not become brittle, and a cured product having good mechanical properties with a high degree of freedom in the shape and application of the molded product can be obtained.

一般式（１）のＸは、硬化物の誘電特性を良好に維持したまま機械的特性を向上させる観点から、熱硬化性樹脂との相溶性が良好な、一般式（２）で示されるものが好ましい。
（一般式（２）において、Ｙは、−ＣＺ２−，−ＣＯ−，−Ｏ−，−Ｓ−または−ＳＯ２−を示しており、一般式（２）および−ＣＺ２−において、Ｚは、−ＣＨ３，−ＣＦ３，−Ｃ２Ｈ５，−Ｆ、または−Ｈを示しており、一般式（２）におけるＹおよび−ＣＺ２−におけるＺはいずれも同一であっても異なっていても良い。Ｚａのａは、Ｚで示される各基の数０〜４を示している。） X in the general formula (1) is the one represented by the general formula (2) having good compatibility with the thermosetting resin from the viewpoint of improving the mechanical properties while maintaining the dielectric properties of the cured product in good condition. Is preferred.
(In General Formula (2), Y represents —CZ 2 —, —CO—, —O—, —S— or —SO 2 —, and in General Formula (2) and —CZ 2 —, Represents —CH 3 , —CF 3 , —C 2 H 5 , —F, or —H, and Y in the general formula (2) and Z in —CZ 2 — are the same or different. A in Za represents the number 0 to 4 of each group represented by Z.)

一般式（１）のイミド基含有ナフトール化合物の水酸基当量は、耐熱性、引張強度、誘電特性を兼ね備えさせるという観点から、２５０〜６００ｇ／ｅｑであることが好ましく、３００〜５５０ｇ／ｅｑであることがより好ましく、３５０〜５００ｇ／ｅｑであることがさらに好ましい。   The hydroxyl equivalent of the imide group-containing naphthol compound of the general formula (1) is preferably 250 to 600 g / eq, and preferably 300 to 550 g / eq from the viewpoint of combining heat resistance, tensile strength, and dielectric properties. Is more preferable, and it is further more preferable that it is 350-500 g / eq.

本発明は、熱硬化性樹脂硬化剤を含有する熱硬化性樹脂組成物としても実施できる。熱硬化性樹脂組成物に含まれる熱硬化性樹脂の例としてエポキシ樹脂が挙げられる。エポキシ樹脂の種類は、特に限定されるものではないが、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールビフェニルアラルキル型エポキシ樹脂、フェノール、ナフトールなどのキシリレン結合によるアラルキル樹脂のエポキシ化物、ジシクロペンタジエン型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂などのグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂などの一分子中にエポキシ基を二個以上有するエポキシ化合物が挙げられる。これらエポキシ樹脂は単独使用でも二種類以上併用してもよい。   The present invention can also be implemented as a thermosetting resin composition containing a thermosetting resin curing agent. An example of the thermosetting resin contained in the thermosetting resin composition is an epoxy resin. The type of epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy Resins, epoxidized aralkyl resins with xylylene bonds such as phenol and naphthol, glycidyl ether type epoxy resins such as dicyclopentadiene type epoxy resin, dihydroxynaphthalene type epoxy resin, triphenolmethane type epoxy resin, glycidyl ester type epoxy resin, glycidyl An epoxy compound having two or more epoxy groups in one molecule such as an amine type epoxy resin can be mentioned. These epoxy resins may be used alone or in combination of two or more.

熱硬化性樹脂としてエポキシ樹脂を含有する熱硬化性樹脂組成物は、熱硬化性樹脂硬化剤が含有しているイミド基含有ナフトール樹脂の水酸基１当量に対して、エポキシ樹脂のエポキシ基が０．８〜１．５当量であることが好ましく、０．９〜１．２当量であることがさらに好ましい。   In the thermosetting resin composition containing an epoxy resin as the thermosetting resin, the epoxy group of the epoxy resin is 0.1% relative to 1 equivalent of the hydroxyl group of the imide group-containing naphthol resin contained in the thermosetting resin curing agent. It is preferably 8 to 1.5 equivalents, and more preferably 0.9 to 1.2 equivalents.

エポキシ樹脂の硬化に際しては、硬化促進剤を併用することが好ましい。かかる硬化促進剤としては、エポキシ樹脂をフェノール系硬化剤で硬化させるための公知の硬化促進剤を用いることができ、例えば、３級アミン化合物、４級アンモニウム塩、イミダゾール類、ホスフィン化合物、ホスホニウム塩などを挙げることができる。より具体的には、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの３級アミン化合物、２−メチルイミダゾール、２，４−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾールなどのイミダゾール類、トリフェニルホスフィン、トリブチルホスフィン、トリ（ｐ−メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィンなどのホスフィン化合物、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラナフトエ酸ボレートなどのホスホニウム塩、トリフェニルホスホニオフェノラート、ベンゾキノンとトリフェニルホスフィンの反応物などのベタイン状有機リン化合物を挙げることができる。とりわけアリーロキシシラン化合物による硬化をスムーズに行う観点から、３級アミン化合物、イミダゾール類、ホスホニウム塩、ベタイン状有機リン化合物の使用が好ましい。   In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenolic curing agent can be used. For example, a tertiary amine compound, a quaternary ammonium salt, an imidazole, a phosphine compound, a phosphonium salt. And so on. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 , 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, tri (p -Phosphine compounds such as methylphenyl) phosphine and tri (nonylphenyl) phosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetranaphthoic acid borate, and triphenylphosphonio Enorato, it may be mentioned betaines like organic phosphorus compounds such as the reaction product of benzoquinone and triphenyl phosphine. In particular, from the viewpoint of smoothly curing with an aryloxysilane compound, it is preferable to use a tertiary amine compound, an imidazole, a phosphonium salt, or a betaine-like organic phosphorus compound.

本実施の形態の熱硬化性樹脂硬化剤にエポキシ樹脂を配合した熱硬化性樹脂組成物における配合比は、エポキシ樹脂硬化剤の反応性官能基／エポキシ樹脂のエポキシ基の当量比が０．５〜１．５、特に０．８〜１．２の範囲であることが好ましい。硬化促進剤は、エポキシ樹脂１００重量部に対して０．１〜５重量部の範囲で使用するのが好ましい。   The compounding ratio in the thermosetting resin composition in which the epoxy resin is blended with the thermosetting resin curing agent of the present embodiment is such that the equivalent ratio of the reactive functional group of the epoxy resin curing agent / the epoxy group of the epoxy resin is 0.5. It is preferably in the range of -1.5, particularly 0.8-1.2. It is preferable to use a hardening accelerator in the range of 0.1-5 weight part with respect to 100 weight part of epoxy resins.

本発明の熱硬化性樹脂組成物は、その配合成分およびその組成比にも依存するが、公知のフェノール系硬化剤を用いた配合で行われる硬化温度同様、例えば１００〜２５０℃の温度範囲で硬化が進行する。   Although the thermosetting resin composition of this invention is dependent also on the compounding component and its composition ratio, it is the temperature range of 100-250 degreeC like the hardening temperature performed by the mixing | blending using a well-known phenol type hardening | curing agent, for example. Curing proceeds.

本発明は、熱硬化性樹脂組成物を硬化させた硬化物として実施することもできる。本実施の形態の硬化物は、高ガラス転移温度と低誘電正接とを両立するから、誘電損失が小さく耐熱性が求められる各種絶縁材料として好適である。本発明の好ましい実施態様として、例えば、多層プリント配線基板の層間絶縁材料が挙げられる。   The present invention can also be carried out as a cured product obtained by curing a thermosetting resin composition. The cured product of the present embodiment is suitable as various insulating materials that have a low dielectric loss and are required to have heat resistance because they have both a high glass transition temperature and a low dielectric loss tangent. As a preferable embodiment of the present invention, for example, an interlayer insulating material of a multilayer printed wiring board can be mentioned.

プリプレグとは、本実施の形態の熱硬化性樹脂組成物をワニスとし、繊維状補強材（基材）に含浸させて、加熱または乾燥させて半硬化状態にしたものをいう。基材としては、ガラスクロス、炭素繊維などが用いられる。熱硬化性樹脂組成物をワニスとし繊維状補強材に含浸させたプリプレグとすることにより、取り扱い性が向上するとともに、硬化させた成形物に繊維状補強材の性質を付与して、硬化物の機械的特性を向上させることができる。   A prepreg refers to a semi-cured state obtained by impregnating a fibrous reinforcing material (base material) with the thermosetting resin composition of the present embodiment as a varnish and heating or drying. As the substrate, glass cloth, carbon fiber, or the like is used. By making a prepreg impregnated with a fibrous reinforcing material using a thermosetting resin composition as a varnish, the handleability is improved and the properties of the fibrous reinforcing material are imparted to the cured molded article. Mechanical properties can be improved.

本実施の形態の熱硬化性樹脂組成物に含有されるイミド基含有ナフトール化合物は、ナフトール化合物がビスマレイミド化合物で連結されている。このため、硬化物が脆くなる一因であるビスマレイミド同士の重合反応が起こらない。したがって、熱硬化性樹脂組成物を用いれば、繊維状補強材などの基材を併用することなく、誘電特性が良好であって、引張弾性率、引張強度、伸び率などの機械的特性の良好な成形物を形成することができる。すなわち、本実施の形態の熱硬化性樹脂組成物は、硬化して得られる硬化物の成形物の自由度が高いことから、例えば、基材を有さない樹脂フィルムなどの原料樹脂として好適である。   In the imide group-containing naphthol compound contained in the thermosetting resin composition of the present embodiment, the naphthol compound is linked with a bismaleimide compound. For this reason, the polymerization reaction between bismaleimides, which contributes to the brittleness of the cured product, does not occur. Therefore, if a thermosetting resin composition is used, the dielectric properties are good without using a substrate such as a fibrous reinforcing material, and mechanical properties such as tensile elastic modulus, tensile strength, and elongation are good. Can be formed. That is, the thermosetting resin composition of the present embodiment is suitable as a raw material resin such as a resin film having no substrate because it has a high degree of freedom in a cured product obtained by curing. is there.

また、本実施の形態の熱硬化性樹脂組成物を硬化させた硬化物は、それ自体の機械的特性が良好である。このため、例えば、熱可塑性樹脂を配合することなく、硬化物からなるガラス転移温度の高い成形物を得ることができる。例えば、本実施の形態の熱硬化性樹脂組成物によれば、ガラス転移温度が２００℃以上の成形物を得ることができる。   Moreover, the cured product obtained by curing the thermosetting resin composition of the present embodiment has good mechanical properties. For this reason, for example, a molded product having a high glass transition temperature made of a cured product can be obtained without blending a thermoplastic resin. For example, according to the thermosetting resin composition of the present embodiment, a molded product having a glass transition temperature of 200 ° C. or higher can be obtained.

本実施の形態の熱硬化性樹脂組成物には、必要に応じて、無機充填剤、カップリング剤、離型剤、着色剤、難燃剤、低応力剤などを添加することができ、また、これらを予め反応して用いることもできる。   In the thermosetting resin composition of the present embodiment, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, and the like can be added as necessary. These can be reacted in advance and used.

無機充填剤の例として、非晶性シリカ、結晶性シリカ、アルミナ、ガラス、珪酸カルシウム、マグネサイト、クレー、タルク、マイカ、マグネシア、硫酸バリウムなどを挙げることができるが、特に非晶性シリカ、結晶性シリカが好ましい。また優れた成形性を維持しつつ無機充填剤の配合量を高めたい場合は、細密充填を可能とするような粒度分布の広い球形の無機充填剤を使用することが好ましい。   Examples of inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesia, barium sulfate, etc., particularly amorphous silica, Crystalline silica is preferred. When it is desired to increase the blending amount of the inorganic filler while maintaining excellent moldability, it is preferable to use a spherical inorganic filler having a wide particle size distribution that enables fine packing.

カップリング剤の例としては、メルカプトシラン系、ビニルシラン系、アミノシラン系、エポキシシラン系などのシランカップリング剤やチタンカップリング剤を、離型剤の例としてはカルナバワックス、パラフィンワックスなど、また着色剤としてはカーボンブラックなどをそれぞれ例示することができる。難燃剤の例としては、リン化合物、金属水酸化物など、低応力剤の例としては、シリコンゴム、変性ニトリルゴム、変性ブタジエンゴム、変性シリコンオイルなどを挙げることができる。   Examples of coupling agents include mercaptosilane-based, vinylsilane-based, aminosilane-based, and epoxysilane-based silane coupling agents and titanium coupling agents. Examples of mold release agents include carnauba wax, paraffin wax, and coloring. Examples of the agent include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

以上のように、本実施の形態のイミド基含有ナフトール樹脂の製造方法は、ナフトール化合物をビスマレイミド化合物で連結するナフトール化ステップにより、ビスマレイミド化合物を含まないイミド基含有ナフトール樹脂とする。これにより、熱硬化性樹脂の硬化反応においてビスマレイミド化合物同士の重合反応が生じることを防止できるから、誘電特性が良好であって、引張弾性率、引張強度、伸び率などの機械的特性が良好な硬化物の原料として有用なイミド基含有ナフトール樹脂を提供することができる。   As mentioned above, the manufacturing method of the imide group containing naphthol resin of this Embodiment makes it the imide group containing naphthol resin which does not contain a bismaleimide compound by the naphtholation step which connects a naphthol compound with a bismaleimide compound. This prevents polymerization reaction between bismaleimide compounds in the curing reaction of the thermosetting resin, so the dielectric properties are good and the mechanical properties such as tensile modulus, tensile strength, and elongation are good. An imide group-containing naphthol resin useful as a raw material for a cured product can be provided.

（実施の形態２）
本実施の形態では、ビスマレイミド化合物同士の重合反応の影響を抑制するために、樹脂組成物に含有されるビスマレイミド化合物とナフトール化合物と配合比を特定し、特定のビスマレイミド化合物を用いる態様で本発明を実施する場合について説明する。 (Embodiment 2)
In this embodiment, in order to suppress the influence of the polymerization reaction between the bismaleimide compounds, the bismaleimide compound and the naphthol compound contained in the resin composition are specified and the specific bismaleimide compound is used. The case of implementing the present invention will be described.

本実施の形態の樹脂組成物は、ビスマレイミド化合物同士の重合反応を抑制するために、ビスマレイミド化合物に対するナフトール化合物の量が過剰になるようにする。この観点から、ビスマレイミド化合物のマレイミド基／ナフトール化合物の水酸基の当量比は、０．１０〜０．４０であることが好ましく、０．２０〜０．３０であることがより好ましい。   In the resin composition of the present embodiment, the amount of the naphthol compound relative to the bismaleimide compound is excessive in order to suppress the polymerization reaction between the bismaleimide compounds. From this viewpoint, the equivalent ratio of the maleimide group of the bismaleimide compound to the hydroxyl group of the naphthol compound is preferably 0.10 to 0.40, and more preferably 0.20 to 0.30.

ビスマレイミド化合物同士の重合反応が生じた場合であっても硬化物が脆くなること（脆化）を抑制する観点から、エーテル結合を有するビスマレイミド化合物を用いることが好ましい。エーテル結合を有するビスマレイミド化合物を用いることにより、ナフトール化ステップを経ていない樹脂組成物を原料として用いて熱硬化させる際に生じるビスマレイミド化合物同士の重合反応による硬化物の脆化を抑制して、引張弾性率、引張強度、伸び率などの機械的特性が良好な硬化物を得ることができる。   Even when a polymerization reaction between bismaleimide compounds occurs, it is preferable to use a bismaleimide compound having an ether bond from the viewpoint of suppressing the brittleness (brittleness) of the cured product. By using a bismaleimide compound having an ether bond, the embrittlement of the cured product due to the polymerization reaction between the bismaleimide compounds generated when the resin composition not subjected to the naphtholization step is used as a raw material is suppressed, A cured product having good mechanical properties such as tensile elastic modulus, tensile strength, and elongation can be obtained.

引張弾性率、引張強度、伸び率などの機械的特性が良好な硬化物を得る観点から、ビスマレイミド化合物が四つの芳香族環を有しており、フェノール樹脂化合物が分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有していることが好ましい。これにより、ナフトール化ステップを経ていない樹脂組成物を原料として用いて機械的特性の良好な硬化物を得ることができる。   From the viewpoint of obtaining a cured product having good mechanical properties such as tensile elastic modulus, tensile strength, and elongation, the bismaleimide compound has four aromatic rings, and the phenol resin compound has two or more in the molecule. It preferably has a hydroxy group and one or more naphthalene skeletons. As a result, a cured product having good mechanical properties can be obtained using a resin composition that has not undergone the naphtholization step as a raw material.

樹脂組成物は、分子中に二つ以上のグリシジル基を有するエポキシ樹脂をさらに含んでいてもよい。エポキシ樹脂をさらに含む場合、樹脂組成物の配合比は、ナフトール化合物の水酸基１当量に対して、マレイミド化合物のマレイミド基とエポキシ樹脂のエポキシ基との合計が０．８〜１．５当量であることが好ましく、０．９〜１．２当量であることがさらに好ましい。   The resin composition may further contain an epoxy resin having two or more glycidyl groups in the molecule. When the epoxy resin is further included, the blending ratio of the resin composition is 0.8 to 1.5 equivalent of the total of the maleimide group of the maleimide compound and the epoxy group of the epoxy resin with respect to 1 equivalent of the hydroxyl group of the naphthol compound. It is preferable that it is 0.9-1.2 equivalent.

以上のとおり、樹脂組成物中のナフトール化合物の配合量をマレイミド化合物に対して過剰とし、特定のマレイミド化合物およびナフトール化合物を用いることにより、マレイミド化合物同士が重合することによる脆化を抑えて、機械的特性の良好な硬化物が得られる。
例えば、エポキシ樹脂を含む樹脂組成物を硬化することにより、良好な機械的特性を備えた硬化物が得られる。したがって、本実施の形態の樹脂組成物は、第１の実施の形態の熱硬化性樹脂組成物同様、硬化して得られる硬化物の成形物の自由度が高く、例えば、基材を有さない樹脂フィルムなどの原料樹脂として好適である。 As described above, the blending amount of the naphthol compound in the resin composition is excessive with respect to the maleimide compound, and by using a specific maleimide compound and a naphthol compound, embrittlement due to polymerization of the maleimide compounds is suppressed, and the machine A cured product with good mechanical properties can be obtained.
For example, a cured product having good mechanical properties can be obtained by curing a resin composition containing an epoxy resin. Therefore, like the thermosetting resin composition of the first embodiment, the resin composition of the present embodiment has a high degree of freedom of a cured product obtained by curing, and has, for example, a substrate. It is suitable as a raw material resin such as a resin film.

以上説明した各実施の形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。このため、上記各実施の形態に開示された各要素は、本発明の技術的範囲に属するすべての設計変更や均等物をも含む趣旨である。   Each embodiment described above is described for facilitating the understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in each of the above embodiments includes all design changes and equivalents belonging to the technical scope of the present invention.

以下に実施例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。以下の実施例および比較例においては、伸び率以外の％は重量％を示している。
（実施例１）
窒素ガス導入管、温度計、撹拌機を備えた四口の３００ｍＬフラスコにナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）７１．６６ｇ、プロピレングリコールモノメチルエーテル５４．０ｇを仕込み、１００℃に昇温して溶解した。次いで、２，２’−ビス−［４−（４−マレイミドフェノキシ）フェニル］プロパン（商品名 ＢＭＩ−４０００、大和化成工業（株）社製）２８．５３ｇを仕込み、１２０℃に昇温して４７時間反応させた。その後、室温まで冷却することで水酸基当量４２９ｇ／ｅｑ、固形分６５．２％のイミド基含有のナフトール樹脂溶液（Ａ−１、イミド基含有ナフトール樹脂の溶液）を得た。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” other than the elongation percentage indicates “wt%”.
Example 1
Naphthol aralkyl resin (trade name: SN-485, hydroxyl group equivalent: 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) in a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, propylene glycol 54.0 g of monomethyl ether was charged and dissolved by heating to 100 ° C. Next, 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (trade name BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 28.53 g was charged, and the temperature was raised to 120 ° C. The reaction was carried out for 47 hours. Thereafter, by cooling to room temperature, an imide group-containing naphthol resin solution (A-1, imide group-containing naphthol resin solution) having a hydroxyl group equivalent of 429 g / eq and a solid content of 65.2% was obtained.

（実施例２）
窒素ガス導入管、温度計、撹拌機を備えた四口の３００ｍＬフラスコにナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）１４３．３３ｇ、プロピレングリコールモノメチルエーテル１０２．８ｇを仕込み、１００℃に昇温して溶解した。次いで、２，２’−ビス−［４−（４−マレイミドフェノキシ）フェニル］プロパン（商品名 ＢＭＩ−４０００、大和化成工業（株）社製）４７．５５ｇを仕込み、１２０℃に昇温して３０時間反応させた。その後、室温まで冷却することで水酸基当量３８２ｇ／ｅｑ、固形分６５．３％のイミド基含有のナフトール樹脂溶液（Ａ−２、イミド基含有ナフトール樹脂の溶液）を得た。 (Example 2)
Naphthol aralkyl resin (trade name: SN-485, hydroxyl group equivalent: 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), propylene glycol, in a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer 102.8 g of monomethyl ether was charged and heated to 100 ° C. to dissolve. Next, 47.55 g of 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane (trade name BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was charged, and the temperature was raised to 120 ° C. The reaction was performed for 30 hours. Thereafter, by cooling to room temperature, an imide group-containing naphthol resin solution (A-2, imide group-containing naphthol resin solution) having a hydroxyl group equivalent of 382 g / eq and a solid content of 65.3% was obtained.

（実施例３〜４、比較例１）
実施例１〜２で得られたイミド基含有のナフトール樹脂溶液（Ａ−１〜Ａ−２）それぞれにビフェニルアラルキル型エポキシ樹脂（商品名 ＮＣ−３０００Ｈ、エポキシ当量２９０ｇ／ｅｑ、日本化薬（株）社製）の固形分７５％のメチルエチルケトン（ＭＥＫ）溶液、２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ）を混合し、樹脂組成物ワニスを作製した（実施例３〜４、熱硬化性樹脂硬化剤、熱硬化性樹脂組成物）。
イミド基含有のナフトール樹脂溶液（Ａ−１〜Ａ−２）に代えて、ナフトールアラルキル樹脂の固形分６５％のプロピレングリコールモノメチルエーテル（ＰＧＭ）溶液を用いて、実施例３〜４と同様にして、樹脂組成物ワニスを作製した（比較例１）。実施例３〜４および比較例１の配合量は表１に記載のとおりであった。さらに銅箔光沢面に樹脂組成物ワニスを塗工し、１００℃で８分間乾燥し、２００℃で６時間硬化させた。硬化後、銅箔から引き剥がして膜厚約８０μｍの硬化物フィルム（硬化物）を得た。 (Examples 3 to 4, Comparative Example 1)
In each of the imide group-containing naphthol resin solutions (A-1 to A-2) obtained in Examples 1 and 2, biphenylaralkyl type epoxy resins (trade name NC-3000H, epoxy equivalent 290 g / eq, Nippon Kayaku Co., Ltd.) (Made)) 75% solid content methyl ethyl ketone (MEK) solution and 2-ethyl-4-methylimidazole (2E4MZ) were mixed to prepare a resin composition varnish (Examples 3 to 4, thermosetting resin curing) Agent, thermosetting resin composition).
In place of the imide group-containing naphthol resin solution (A-1 to A-2), a propylene glycol monomethyl ether (PGM) solution having a solid content of naphthol aralkyl resin of 65% was used in the same manner as in Examples 3 to 4. A resin composition varnish was prepared (Comparative Example 1). The compounding amounts of Examples 3 to 4 and Comparative Example 1 were as shown in Table 1. Furthermore, the resin composition varnish was applied to the glossy surface of the copper foil, dried at 100 ° C. for 8 minutes, and cured at 200 ° C. for 6 hours. After curing, it was peeled off from the copper foil to obtain a cured film (cured product) having a film thickness of about 80 μm.

（ガラス転移点の測定）
実施例３〜４、および比較例１で得られた硬化物フィルムを、所定の大きさにカット（切り出）してガラス転移点測定のサンプルとした。以下の条件にてサンプルのガラス転移温度を測定した。
測定機器 ：リガク社製 熱機械分析装置ＴＭＡ８３１０ｅｖｏ
サンプル寸法：幅５ｍｍ×長さ１５ｍｍ×厚さ０．０８０ｍｍ（８０μｍ）
雰囲気 ：窒素中
測定温度 ：２５〜３００℃
昇温速度 ：１０℃／ｍｉｎ．
測定モ−ド ：引張
（引張弾性率、引張強度、伸び率の測定）
実施例３〜４、および比較例１で得られた硬化物フィルムを、所定の大きさにカットして測定用のサンプルとした。以下の条件にてサンプルの引張弾性率、引張強度、伸び率を測定した。
測定機器：島津製作所製オートグラフＡＧ−Ｘｐｌｕｓ
引張速度：５ｍｍ／ｍｉｎ．
サンプル寸法：幅１０ｍｍ×長さ１５０ｍｍ×厚さ０．０８０ｍｍ（８０μｍ）
（誘電特性の評価）
作製した硬化物フィルムを所定の大きさに切り出して、測定用のサンプルとした。下記の測定機器を用いて、以下の条件にてサンプルの誘電特性を測定した。
測定機器：キーサイトテクノロジー社製 ネットワークアナライザーＥ５０７１Ｃ
関東電子応用開発社製 空洞共振器摂動法誘電率測定装置
周波数 ：１ＧＨｚ
サンプル寸法：幅２ｍｍ×長さ１００ｍｍ×厚さ０．０８０ｍｍ（８０μｍ） (Measurement of glass transition point)
The cured product films obtained in Examples 3 to 4 and Comparative Example 1 were cut (cut out) to a predetermined size to obtain glass transition point measurement samples. The glass transition temperature of the sample was measured under the following conditions.
Measuring instrument: Thermomechanical analyzer TMA8310evo manufactured by Rigaku
Sample dimensions: width 5 mm x length 15 mm x thickness 0.080 mm (80 μm)
Atmosphere: In nitrogen Measurement temperature: 25-300 ° C
Temperature increase rate: 10 ° C./min.
Measurement mode: Tensile (measurement of tensile modulus, tensile strength, elongation)
The cured product films obtained in Examples 3 to 4 and Comparative Example 1 were cut to a predetermined size to obtain measurement samples. The tensile modulus, tensile strength, and elongation of the sample were measured under the following conditions.
Measuring equipment: Shimadzu Autograph AG-Xplus
Tensile speed: 5 mm / min.
Sample dimensions: width 10 mm x length 150 mm x thickness 0.080 mm (80 μm)
(Evaluation of dielectric properties)
The produced cured product film was cut into a predetermined size and used as a sample for measurement. The dielectric properties of the samples were measured using the following measuring equipment under the following conditions.
Measuring instrument: Network analyzer E5071C manufactured by Keysight Technology
Cavity resonator perturbation method dielectric constant measuring device manufactured by Kanto Electronics Application Development Co.
Frequency: 1GHz
Sample dimensions: width 2 mm x length 100 mm x thickness 0.080 mm (80 μm)

表１中、配合量は固形分換算値であり、単位は重量部である。
表１に示したように、実施例１および２のイミド基含有ナフトール樹脂を熱硬化性樹脂として含む熱硬化性樹脂組成物を硬化させた実施例３および４の硬化物フィルムはいずれも、誘電特性（誘電率、誘電正接）および機械的特性（引張弾性率、引張強度、伸び率）に優れていた。また、ガラス転移点も２００℃以上と高く良好であった。 In Table 1, the compounding amount is a solid content conversion value, and the unit is parts by weight.
As shown in Table 1, the cured films of Examples 3 and 4 obtained by curing the thermosetting resin composition containing the imide group-containing naphthol resin of Examples 1 and 2 as a thermosetting resin are both dielectric. Excellent properties (dielectric constant, dielectric loss tangent) and mechanical properties (tensile elastic modulus, tensile strength, elongation). Moreover, the glass transition point was also high and favorable at 200 degreeC or more.

（実施例５）
ナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）の固形分６５％のＰＧＭ溶液８２．６９ｇ、２，２’−ビス−［４−（４−マレイミドフェノキシ）フェニル］プロパン（商品名 ＢＭＩ−４０００、大和化成工業（株）社製）１７．８３ｇ、ビフェニルアラルキル型エポキシ樹脂（商品名 ＮＣ−３０００Ｈ、エポキシ当量２９０ｇ／ｅｑ、日本化薬（株）社製）の７５％ＭＥＫ溶液 ８７．００ｇを混合し、Ｎ，Ｎ−ジメチルアセトアミドを添加しながら常温で溶解することで樹脂組成物ワニス（Ｂ−１、樹脂組成物）を得た。 (Example 5)
Naphthol aralkyl resin (trade name SN-485, hydroxyl group equivalent 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) with a solid content of 65% PGM solution 82.69 g, 2,2′-bis- [4- (4- Maleimidophenoxy) phenyl] propane (trade name BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 17.83 g, biphenyl aralkyl type epoxy resin (trade name NC-3000H, epoxy equivalent 290 g / eq, Nippon Kayaku Co., Ltd.) A resin composition varnish (B-1, resin composition) was obtained by mixing 87.00 g of a 75% MEK solution (manufactured by Kogyo Co., Ltd.) and dissolving at room temperature while adding N, N-dimethylacetamide.

（実施例６）
ナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）の固形分６５％のＰＧＭ溶液８２．６９ｇ、ビス（４−マレイミドフェニル）メタン（商品名 ＢＭＩ−Ｈ、ケイアイ化成（株）社製）１１．２０ｇ、ビフェニルアラルキル型エポキシ樹脂（商品名 ＮＣ−３０００Ｈ、エポキシ当量２９０ｇ／ｅｑ、日本化薬（株）社製）の７５％ＭＥＫ溶液 ８７．００ｇを混合し、Ｎ，Ｎ−ジメチルアセトアミドを添加しながら常温で溶解することで樹脂組成物ワニス（Ｂ−２、樹脂組成物）を得た。 (Example 6)
Naphthol aralkyl resin (trade name SN-485, hydroxyl equivalent 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) with a solid content of 65% PGM solution 82.69 g, bis (4-maleimidophenyl) methane (trade name BMI- 11.20 g of H, manufactured by KAI Kasei Co., Ltd., 87.00 g of a 75% MEK solution of biphenyl aralkyl type epoxy resin (trade name NC-3000H, epoxy equivalent 290 g / eq, manufactured by Nippon Kayaku Co., Ltd.) By mixing and dissolving at room temperature while adding N, N-dimethylacetamide, a resin composition varnish (B-2, resin composition) was obtained.

（実施例７）
窒素ガス導入管、温度計、撹拌機を備えた四口の３００ｍＬフラスコにナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）５３．７５ｇ、ビス（４−マレイミドフェニル）メタン（商品名 ＢＭＩ−Ｈ、ケイアイ化成（株）社製）１１．２０ｇ、ビフェニルアラルキル型エポキシ樹脂（商品名 ＮＣ−３０００Ｈ、エポキシ当量２９０ｇ／ｅｑ、日本化薬（株）社製）６５．２５、ＭＥＫ ８６．８ｇを仕込み、溶解しながら８０℃に昇温した。さらに８０℃の温度で６時間保持した後に室温まで冷却することで、樹脂組成物ワニス（Ｂ−３、樹脂組成物）を得た。 (Example 7)
Naphthol aralkyl resin (trade name SN-485, hydroxyl group equivalent 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 53.75 g, bis ( 4-maleimidophenyl) methane (trade name BMI-H, manufactured by KAI Kasei Co., Ltd.) 11.20 g, biphenyl aralkyl type epoxy resin (trade name NC-3000H, epoxy equivalent 290 g / eq, Nippon Kayaku Co., Ltd.) (Made) 65.25 and MEK 86.8g were charged, and it heated up at 80 degreeC, melt | dissolving. Furthermore, after hold | maintaining at the temperature of 80 degreeC for 6 hours, the resin composition varnish (B-3, resin composition) was obtained by cooling to room temperature.

（比較例２）
窒素ガス導入管、温度計、撹拌機を備えた四口の３００ｍＬフラスコナフトールアラルキル樹脂（商品名 ＳＮ−４８５、水酸基当量２１５ｇ／ｅｑ、新日鉄住金化学（株）社製）１５．０ｇ、ビス（４−マレイミドフェニル）メタン（商品名 ＢＭＩ−Ｈ、ケイアイ化成（株）社製）６０．０ｇ、ビフェニルアラルキル型エポキシ樹脂（商品名 ＮＣ−３０００Ｈ、エポキシ当量２９０ｇ／ｅｑ、日本化薬（株）社製）２５．０ｇ、ＭＥＫ ６６．７ｇを仕込み、溶解しながら８０℃に昇温した。さらに８０℃の温度で１７時間保持した後に室温まで冷却することで、樹脂組成物ワニス（Ｂ−４）を得た。 (Comparative Example 2)
Four-necked 300 mL flask naphthol aralkyl resin (trade name SN-485, hydroxyl equivalent 215 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 15.0 g, screw (4 -Maleimidophenyl) methane (trade name: BMI-H, manufactured by Keisei Kasei Co., Ltd.), 60.0 g, biphenyl aralkyl type epoxy resin (trade name: NC-3000H, epoxy equivalent: 290 g / eq, manufactured by Nippon Kayaku Co., Ltd.) ) 25.0 g and MEK 66.7 g were charged and heated to 80 ° C. while dissolving. Furthermore, after hold | maintaining at the temperature of 80 degreeC for 17 hours, the resin composition varnish (B-4) was obtained by cooling to room temperature.

（実施例８〜１０、比較例３）
実施例５〜７で得られた樹脂組成物ワニス（Ｂ−１〜Ｂ−３）それぞれに、硬化促進剤２Ｅ４ＭＺを樹脂組成物ワニス固形分に対して０．３ｐｈｒ添加して混合した。配合量は表２に記載のとおりであった。さらに銅箔光沢面に樹脂組成物ワニスを塗工し、１００℃で８分間乾燥し、２００℃で６時間硬化させた。硬化後、銅箔から引き剥がして膜厚約８０μｍの硬化物フィルムを得た（実施例８〜１０）。
実施例５〜７で得られた樹脂組成物ワニス（Ｂ−１〜Ｂ−３）の代わりに、比較例２で得られた樹脂組成物ワニス（Ｂ−４）を用いて、実施例８〜１０と同様にして、膜厚約８０μｍの硬化物フィルムを得た（比較例３）。
表２中、配合量は固形分換算値であり、単位は重量部である。測定不能は、硬化物が脆く引張試験を実施することができなかったことを示す。
表２に示すように、マレイミド基に対する水酸基が過剰となるように含有量が調整されたビスマレイミド化合物とナフトール化合物とを含んだ樹脂組成物である実施例８〜１０はいずれも、良好な誘電特性および機械的特性を示した。これら実施例の中でも特に、エーテル結合および四つの芳香族環を有しているビスマレイミド化合物を含む実施例８の樹脂組成物を硬化させた硬化物である硬化物フィルムは、引張弾性率が良好であって、またガラス転移点が高く、耐熱性の成形品として高い性能を備えていた。 (Examples 8 to 10, Comparative Example 3)
To each of the resin composition varnishes (B-1 to B-3) obtained in Examples 5 to 7, 0.3 phr of the curing accelerator 2E4MZ was added to and mixed with the resin composition varnish solid content. The blending amount was as shown in Table 2. Furthermore, the resin composition varnish was applied to the glossy surface of the copper foil, dried at 100 ° C. for 8 minutes, and cured at 200 ° C. for 6 hours. After curing, it was peeled off from the copper foil to obtain a cured product film having a thickness of about 80 μm (Examples 8 to 10).
Instead of the resin composition varnishes (B-1 to B-3) obtained in Examples 5 to 7, the resin composition varnish (B-4) obtained in Comparative Example 2 was used, and Examples 8 to In the same manner as in Example 10, a cured product film having a thickness of about 80 μm was obtained (Comparative Example 3).
In Table 2, the compounding amount is a solid content conversion value, and the unit is parts by weight. Inability to measure indicates that the cured product was brittle and the tensile test could not be performed.
As shown in Table 2, Examples 8 to 10, which are resin compositions containing a bismaleimide compound and a naphthol compound whose contents are adjusted so that the hydroxyl group with respect to the maleimide group is excessive, are all good dielectrics. The properties and mechanical properties are shown. Among these examples, the cured film, which is a cured product obtained by curing the resin composition of Example 8 containing a bismaleimide compound having an ether bond and four aromatic rings, has a good tensile modulus. In addition, the glass transition point is high, and it has high performance as a heat-resistant molded product.

本発明により提供されるイミド基含有ナフトール樹脂、熱硬化性樹脂組成物は、電気電子産業を中心に各種の分野における絶縁材料として有用である。熱硬化性樹脂組成物を硬化させて得られる硬化物は、誘電特性および機械的特性が良好であるため、基材を併用しなくても十分な機械的特性を備えた種々の成形品を形成する原料として有用である。   The imide group-containing naphthol resin and thermosetting resin composition provided by the present invention are useful as insulating materials in various fields mainly in the electric and electronics industry. The cured product obtained by curing the thermosetting resin composition has good dielectric and mechanical properties, so various molded products with sufficient mechanical properties can be formed without using a substrate. It is useful as a raw material.

Claims (14)

ナフトール化合物の水酸基１当量に対して、ビスマレイミド化合物のマレイミド基０．１０〜０．４０当量を反応させて前記ナフトール化合物を前記ビスマレイミド化合物で連結するナフトール化ステップを備えているイミド基含有ナフトール樹脂の製造方法。 On 1 equivalent of hydroxyl group of the naphthol compound, bismaleimide compound maleimide groups 0.10 to 0.40 imide-containing naphthol and a naphthol of steps for connecting with the bismaleimide compound the naphthol compound is reacted with eq Manufacturing method of resin. 前記ナフトール化合物は、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有する請求項１に記載のイミド基含有ナフトール樹脂の製造方法。   The method for producing an imide group-containing naphthol resin according to claim 1, wherein the naphthol compound has two or more hydroxy groups and one or two or more naphthalene skeletons in a molecule. 前記ビスマレイミド化合物は、エーテル結合および四つの芳香族環を有する請求項１または２に記載のイミド基含有ナフトール樹脂の製造方法。   The method for producing an imide group-containing naphthol resin according to claim 1 or 2, wherein the bismaleimide compound has an ether bond and four aromatic rings. 前記ナフトール化ステップは、前記ナフトール化合物と前記ビスマレイミド化合物とを溶媒中で加熱するステップである請求項１〜３のいずれか一項に記載のイミド基含有ナフトール樹脂の製造方法。   The method for producing an imide group-containing naphthol resin according to any one of claims 1 to 3, wherein the naphtholation step is a step of heating the naphthol compound and the bismaleimide compound in a solvent. ナフトール化合物の水酸基１当量に対して、ビスマレイミド化合物のマレイミド基０．１０〜０．４０当量を反応させて前記ナフトール化合物を前記ビスマレイミド化合物で連結するナフトール化ステップを備えている、イミド基含有ナフトール樹脂を含有する熱硬化性樹脂硬化剤の製造方法。 On 1 equivalent of hydroxyl group of the naphthol compound, a naphthol of steps for connecting the naphthol compound the bis-maleimide compound is reacted maleimide groups 0.10 to 0.40 equivalents of bis-maleimide compound, containing the imide group A method for producing a thermosetting resin curing agent containing a naphthol resin. 水酸基当量が２５０〜６００ｇ／ｅｑである、請求項５に記載の熱硬化性樹脂硬化剤の製造方法。   The manufacturing method of the thermosetting resin hardening | curing agent of Claim 5 whose hydroxyl equivalent is 250-600 g / eq. ビスマレイミド化合物とナフトール化合物とを含んでおり、
前記ナフトール化合物の水酸基１当量に対して、前記ビスマレイミド化合物のマレイミド基が０．１０〜０．４０当量であり、
前記ビスマレイミド化合物が、エーテル結合および四つの芳香族環を有しており、
前記ナフトール化合物が、分子中に二つ以上のヒドロキシ基および、一つまたは二つ以上のナフタレン骨格を有している樹脂組成物。 A bismaleimide compound and a naphthol compound,
The maleimide group of the bismaleimide compound is 0.10 to 0.40 equivalent with respect to 1 equivalent of the hydroxyl group of the naphthol compound,
The bismaleimide compound has an ether bond and four aromatic rings;
The resin composition in which the naphthol compound has two or more hydroxy groups and one or two or more naphthalene skeletons in a molecule. さらに分子中に二つ以上のグリシジル基を有するエポキシ樹脂を含んでおり、
前記ナフトール化合物の水酸基１当量に対して、前記マレイミド化合物のマレイミド基当量と前記エポキシ樹脂のエポキシ基当量との合計が０．８〜１．５当量である請求項７に記載の樹脂組成物。 Furthermore, it contains an epoxy resin having two or more glycidyl groups in the molecule,
The resin composition according to claim 7, wherein the total of the maleimide group equivalent of the maleimide compound and the epoxy group equivalent of the epoxy resin is 0.8 to 1.5 equivalents relative to 1 equivalent of the hydroxyl group of the naphthol compound. 請求項７または８に記載の樹脂組成物を含有している熱硬化性樹脂組成物。   A thermosetting resin composition containing the resin composition according to claim 7 or 8. さらに硬化促進剤を含む請求項９に記載の熱硬化性樹脂組成物。 Furthermore, the thermosetting resin composition of Claim 9 containing a hardening accelerator. さらに無機充填材を含む請求項９または１０のいずれか一項に記載の熱硬化性樹脂組成物。 Furthermore, the thermosetting resin composition as described in any one of Claim 9 or 10 containing an inorganic filler. 請求項９〜１１のいずれか一項に記載の熱硬化性樹脂組成物を硬化させた硬化物。 Hardened | cured material which hardened the thermosetting resin composition as described in any one of Claims 9-11 . 請求項９〜１１のいずれか一項に記載の熱硬化性樹脂組成物からなる層間絶縁材料。 The interlayer insulation material which consists of a thermosetting resin composition as described in any one of Claims 9-11 . 請求項９〜１１のいずれか一項に記載の熱硬化性樹脂を、繊維状補強材に含浸させ加熱乾燥し、半硬化させて得られたプリプレグ。 A prepreg obtained by impregnating the thermosetting resin according to any one of claims 9 to 11 into a fibrous reinforcing material, heat drying, and semi-curing.
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