JP2008163068A - Cationically polymerizable resin composition for molded article, and molded article by using the same - Google Patents

Cationically polymerizable resin composition for molded article, and molded article by using the same Download PDF

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JP2008163068A
JP2008163068A JP2006351026A JP2006351026A JP2008163068A JP 2008163068 A JP2008163068 A JP 2008163068A JP 2006351026 A JP2006351026 A JP 2006351026A JP 2006351026 A JP2006351026 A JP 2006351026A JP 2008163068 A JP2008163068 A JP 2008163068A
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resin composition
epoxy compound
molded article
cationically polymerizable
polymerizable resin
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O Shibata
欧 柴田
Sachiko Fujita
幸子 藤田
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DH Material Inc
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DH Material Inc
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Priority to PCT/JP2007/074690 priority patent/WO2008078692A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having an excellent alcohol resistance which is a problem in thermosetting resins represented by conventional unsaturated polyester resins and vinyl ester resins, especially resistance to methanol, and also excellent in heat resistance and molding processability, and a molded article by using the same. <P>SOLUTION: This cationically polymerizable resin composition is characterized by containing (A) 70 to 99 pts.mass epoxy compound having 2 to 4 epoxy groups and also having an aromatic backbone, (B) 1 to 30 pts.mass aromatic monomer having 1 to 2 vinyl groups and (C) a cationic curing agent, wherein, the mixture consisting of (A) the epoxy compound and (B) the aromatic monomer in the above mass ratio is a liquid state at a normal temperature (25°C). The molded article is characterized in that it is obtained by curing the above cationically polymerizable resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、耐アルコール性、耐熱性、成形加工性に優れた成形品用カチオン重合性樹脂組成物およびそれを用いた成形品に関するものである。   The present invention relates to a cationic polymerizable resin composition for molded articles having excellent alcohol resistance, heat resistance, and molding processability, and a molded article using the same.

近年、植物由来のバイオエタノールの生産が開始され、こうしたエタノールを貯蔵するための成形品としてはポリオレフィン系成形品が使用されているが、剛性が十分得られない欠点があった。
一般的に剛性のある成形品に使用される樹脂としては、耐熱性、耐薬品性、耐蝕性に優れることから不飽和ポリエステル樹脂、ビニルエステル樹脂等の熱硬化性樹脂が知られ、この樹脂をラジカル系硬化剤、充填剤、繊維強化材と共に使用し、様々な用途、例えば、槽、パイプ、板、船体、住設機器、自動車部材等の成形品に使用されることが知られている（特許文献１参照）。 In recent years, production of plant-derived bioethanol has been started, and polyolefin-based molded products are used as molded products for storing such ethanol, but there is a drawback that sufficient rigidity cannot be obtained.
As resins used for rigid molded products, thermosetting resins such as unsaturated polyester resins and vinyl ester resins are known because of their excellent heat resistance, chemical resistance, and corrosion resistance. It is known that it is used together with radical curing agents, fillers, fiber reinforcements, and used in various applications, for example, molded articles such as tanks, pipes, plates, hulls, housing equipment, and automobile members ( Patent Document 1).

また、上記以外の樹脂として、例えば、エポキシ樹脂は、光・電子線等放射線で硬化するエポキシ塗料又は接着剤として、エポキシ化合物と光硬化性カチオン系硬化剤とからなる重合性組成物が知られている（特許文献２および３参照）。
特開２００３−１９２７５３号公報 特開平０３−１７１０１号公報 特開平１１−３０２３５８号公報 In addition, as a resin other than the above, for example, an epoxy resin is known as a polymerizable composition comprising an epoxy compound and a photocurable cationic curing agent as an epoxy paint or adhesive that is cured by radiation such as light and electron beams. (See Patent Documents 2 and 3).
JP 2003-192753 A Japanese Patent Laid-Open No. 03-17101 Japanese Patent Laid-Open No. 11-302358

しかしながら、前記熱硬化性樹脂では、極性溶剤であるメタノールおよびエタノール類に対する耐アルコール性に関して十分ではなく、特に長期耐久性を要求される場合には、実用上使用できなかった。
また、前記エポキシ樹脂では、耐アルコール性に関する成形品としての検討については知られていない。 However, the thermosetting resin is not sufficient in terms of alcohol resistance against methanol and ethanol, which are polar solvents, and cannot be used practically when long-term durability is required.
Moreover, in the said epoxy resin, it is not known about the examination as a molded article regarding alcohol resistance.

本発明の目的は、従来の不飽和ポリエステル樹脂、ビニルエステル樹脂に代表される熱硬化性樹脂において問題であった耐アルコール性、特にメタノールに対する優れた耐久性を有し、また耐熱性、成形加工性にも優れる樹脂組成物およびそれを用いた成形品を提供することにある。   The object of the present invention is to have alcohol resistance, particularly excellent durability against methanol, which has been a problem in conventional thermosetting resins represented by unsaturated polyester resins and vinyl ester resins, as well as heat resistance and molding processing. It is providing the resin composition which is excellent also in a property, and a molded article using the same.

即ち、本発明者らは、メタノールおよびエタノール等のアルコール類に対して十分な耐久性を有すると共に、優れた成形加工性および耐熱性等の従来の熱硬化性樹脂の優れた特性を維持できる成形品用樹脂について研究した結果、特定の樹脂骨格、粘度を有するエポキシ化合物と、特定の骨格を有する単量体との組み合わせにより、成形加工性に必要な樹脂粘度および耐熱性を維持したまま、従来達成できなかった耐アルコール性に優れる成形品用カチオン重合性樹脂組成物を完成するに至った。   That is, the present inventors have sufficient durability against alcohols such as methanol and ethanol, and can maintain the excellent properties of conventional thermosetting resins such as excellent moldability and heat resistance. As a result of research on resins for products, it has been known that the resin viscosity and heat resistance required for molding processability are maintained by combining a specific resin skeleton, an epoxy compound having a viscosity, and a monomer having a specific skeleton. It came to complete the cationically polymerizable resin composition for molded articles which was excellent in alcohol resistance which was not able to be achieved.

即ち、本発明は、エポキシ基を２〜４個含有しかつ芳香族系骨格を有するエポキシ化合物（Ａ）７０〜９９質量部、ビニル基を１〜２個有する芳香族系単量体（Ｂ）１〜３０質量部及びカチオン系硬化剤（Ｃ）を含有し、前記エポキシ化合物（Ａ）及び前記芳香族系単量体（Ｂ）の前記質量比における混合物が常温（２５℃）で液状であることを特徴とする成形品用カチオン重合性樹脂組成物、及び係る成形品用カチオン重合性樹脂組成物を硬化せしめて得られることを特徴とする成形品を提供するものである。   That is, the present invention comprises an epoxy compound (A) having 2 to 4 epoxy groups and an aromatic skeleton (A) 70 to 99 parts by mass, and an aromatic monomer (B) having 1 to 2 vinyl groups. 1-30 mass parts and a cationic hardening | curing agent (C) are contained, The mixture in the said mass ratio of the said epoxy compound (A) and the said aromatic monomer (B) is liquid at normal temperature (25 degreeC). The present invention provides a cation polymerizable resin composition for molded articles characterized by the above, and a molded article obtained by curing the cation polymerizable resin composition for molded articles.

本発明は、従来の不飽和ポリエステル樹脂或いはビニルエステル樹脂等の熱硬化性樹脂に於いて問題であつたメタノールに代表されるアルコールに対する優れた耐久性を保持し、また耐熱性および成形加工性を両立できる成形品用樹脂組成物により、耐アルコール性に優れた各種成形品を提供することができるので非常に有用である。   The present invention retains excellent durability against alcohol typified by methanol, which has been a problem in conventional thermosetting resins such as unsaturated polyester resins or vinyl ester resins, and also has heat resistance and moldability. Since the resin composition for molded articles that can be compatible with each other can provide various molded articles having excellent alcohol resistance, it is very useful.

本発明において、エポキシ基を２個〜４個含有しかつ芳香族系骨格を有するエポキシ化合物（Ａ）とは、特に限定されないが、好ましくは前記芳香族系単量体（Ｂ）と相溶する２５℃で液状の化合物、或いは前記芳香族系単量体（Ｂ）に溶解する固体の化合物である。さらには、芳香族主鎖骨格の末端にエポキシ基を２個〜４個有するものが好ましく、例えば、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＳ等とエピクロロヒドリンとから誘導されるビスフェノール型エポキシ樹脂、フェノールノボラック又はクレゾールノボラック等から誘導されるノボラック型エポキシ樹脂等が挙げられる。好ましくはビスフェノール型エポキシ樹脂である。
２５℃で液状のエポキシ化合物とは、２５℃で流動性を有する粘度を持つもののことを言い、２５℃での粘度が０．１〜３００Ｐａ・ｓであることが好ましく、より好ましくは０．１〜１００Ｐａ・ｓである。またエポキシ当量としては、好ましくは１００〜１０００（ｇ／ｅｑ．）、より好ましくは１５０〜３００（ｇ／ｅｑ．）である。
該（Ａ）は、本発明の樹脂組成物中に７０〜９９質量部含まれ、好ましくは８０〜９９質量部含まれる。 In the present invention, the epoxy compound (A) containing 2 to 4 epoxy groups and having an aromatic skeleton is not particularly limited, but is preferably compatible with the aromatic monomer (B). A compound that is liquid at 25 ° C. or a solid compound that dissolves in the aromatic monomer (B). Furthermore, those having 2 to 4 epoxy groups at the end of the aromatic main chain skeleton are preferable. For example, bisphenol type epoxy resin derived from bisphenol A, bisphenol F or bisphenol S and epichlorohydrin, Examples thereof include novolak type epoxy resins derived from phenol novolak or cresol novolak. Bisphenol type epoxy resins are preferred.
The epoxy compound which is liquid at 25 ° C. means a compound having fluidity at 25 ° C., and the viscosity at 25 ° C. is preferably 0.1 to 300 Pa · s, more preferably 0.1 ~ 100 Pa · s. Moreover, as an epoxy equivalent, Preferably it is 100-1000 (g / eq.), More preferably, it is 150-300 (g / eq.).
The (A) is contained in the resin composition of the present invention in an amount of 70 to 99 parts by mass, preferably 80 to 99 parts by mass.

芳香族系骨格を含有しないエポキシ化合物、例えば、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂、種々高分子中の二重結合を過酸化物等によりエポキシ化することにより得られるエポキシ基を有するエポキシ化合物は、耐アルコール性および耐熱性の観点から好ましくない。本発明において、芳香族系骨格を有する特定のエポキシ化合物を使用することにより、優れた耐熱性、耐アルコール性の両立が達成できる。エポキシ化合物のエポキシ基の数が１個では、耐熱性、耐アルコール性において好ましくなく、５個以上では、得られる成形品の物性上非常に脆いものとなり好ましくない。   Epoxy compounds that do not contain an aromatic skeleton, such as alicyclic epoxy resins, aliphatic epoxy resins, and epoxies having an epoxy group obtained by epoxidizing double bonds in various polymers with peroxides, etc. Compounds are not preferred from the viewpoints of alcohol resistance and heat resistance. In the present invention, both excellent heat resistance and alcohol resistance can be achieved by using a specific epoxy compound having an aromatic skeleton. When the number of epoxy groups in the epoxy compound is 1, it is not preferable in terms of heat resistance and alcohol resistance, and when it is 5 or more, it is not preferable because the resulting molded article is very brittle.

エポキシ化合物（Ａ）の具体例としては、例えば、ジグリシジルオルトフタレート、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、フェノールノボラックポリグリシジルエーテル、クレゾールノボラックポリグリシジルエーテル、ビフェニルポリグリシジルエーテル、ナフタレンポリグリシジルエーテル等のエポキシ化合物が挙げられる。耐アルコール性および耐熱性の観点から、ビスフェノール型、ノボラック型エポキシ化合物の使用が好ましい。また成形加工性に影響する粘度の観点からは、ビスフェノールＦ型、ビスフェノールＡ型エポキシ化合物が特に好ましい。   Specific examples of the epoxy compound (A) include, for example, diglycidyl orthophthalate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, biphenyl polyglycidyl ether, and naphthalene polyglycidyl. An epoxy compound such as ether can be used. From the viewpoint of alcohol resistance and heat resistance, it is preferable to use a bisphenol type or novolac type epoxy compound. Further, from the viewpoint of the viscosity affecting the moldability, bisphenol F type and bisphenol A type epoxy compounds are particularly preferable.

また、本発明の樹脂組成物には、本発明の効果を損なわない範囲で、脂環式エポキシ樹脂、脂肪族系エポキシ樹脂を併用することも可能である。   The resin composition of the present invention can be used in combination with an alicyclic epoxy resin and an aliphatic epoxy resin as long as the effects of the present invention are not impaired.

本発明において、ビニル基を１〜２個有する芳香族系単量体（Ｂ）とは、カチオン系硬化剤（Ｃ）により硬化しうる化合物で骨格中に二重結合（ビニル基）を有する２５℃で液状の芳香族系化合物をいい、例えば、スチレン、ビニルトルエン、ジビニルベンゼン等が例示され、スチレン、ジビニルベンゼンが好ましく、特にジビニルベンゼンが好ましい。この単量体（Ｂ）は、耐アルコール性および耐熱性を損なうことなく、成形加工にて要求される樹脂粘度を調整する目的での希釈剤としての役割を果たすものであること、更に架橋効果の点から、ビニル基を２個有する芳香族系単量体が好ましい。特に、ジビニルベンゼンは、化合物中に酸素原子等の所謂、極性成分を有さず、二官能架橋モノマーとして働き、良好な成形加工性を保つために必要な樹脂組成物の粘度調整剤としての役割ばかりでなく、耐アルコール性にとっても有用である。上記芳香族系単量体（Ｂ）は、単独で使用してもよいし２種類以上を組み合わせて使用してもよい。２種類以上を組み合わせて使用する場合は、スチレン及びジビニルベンゼンの組み合わせが好ましい。
一般に知られているカチオン重合系樹脂においては、希釈剤として芳香族系骨格を有さないビニルエーテル系化合物が用いられる場合があるが、本発明の耐熱性、耐アルコール性の両立を達成するためには、好ましくない。該（Ｂ）は、本発明の樹脂組成物中に１〜３０質量部含まれ、好ましくは１〜２０質量部含まれる。また、前記エポキシ化合物（Ａ）を溶解する他の単量体を本発明の効果を損なわない範囲で併用することができる。 In the present invention, the aromatic monomer (B) having 1 to 2 vinyl groups is a compound that can be cured by a cationic curing agent (C) and has a double bond (vinyl group) in the skeleton. An aromatic compound that is liquid at 0 ° C. includes, for example, styrene, vinyltoluene, divinylbenzene, and the like. Styrene and divinylbenzene are preferable, and divinylbenzene is particularly preferable. This monomer (B) plays a role as a diluent for the purpose of adjusting the resin viscosity required in molding without impairing the alcohol resistance and heat resistance, and further has a crosslinking effect. From this point, an aromatic monomer having two vinyl groups is preferred. In particular, divinylbenzene does not have a so-called polar component such as an oxygen atom in the compound, functions as a bifunctional crosslinking monomer, and serves as a viscosity modifier for a resin composition necessary for maintaining good molding processability. Not only is it useful for alcohol resistance. The said aromatic monomer (B) may be used independently and may be used in combination of 2 or more types. When two or more types are used in combination, a combination of styrene and divinylbenzene is preferable.
In a generally known cationic polymerization resin, a vinyl ether compound having no aromatic skeleton may be used as a diluent, but in order to achieve both the heat resistance and alcohol resistance of the present invention. Is not preferred. The (B) is contained in the resin composition of the present invention in an amount of 1 to 30 parts by mass, preferably 1 to 20 parts by mass. Moreover, the other monomer which melt | dissolves the said epoxy compound (A) can be used together in the range which does not impair the effect of this invention.

本発明において、カチオン系硬化剤（Ｃ）としては、熱あるいは紫外線照射によりブレンステッド酸を発生し、エポキシ化合物およびビニル基含有芳香族系単量体を重合させることができる公知慣用のものが何れも使用できる。例えば、カチオン部分が、芳香族スルホニウム及び芳香族ヨードニウムからなる群から選ばれる何れかであり、アニオン部分が、ＢＦ４ −、ＰＦ６ −、ＳｂＦ６ −等で構成されるオニウム塩が挙げられる。 In the present invention, as the cationic curing agent (C), any known one that can generate a Bronsted acid by heat or ultraviolet irradiation to polymerize an epoxy compound and a vinyl group-containing aromatic monomer can be used. Can also be used. For example, the cationic portion is, is either selected from the group consisting of aromatic sulfonium and aromatic iodonium, anion portion, BF 4 -, PF 6 - , SbF 6 - and the like constitute an onium salt or the like.

カチオン系硬化剤（Ｃ）の具体例としては、例えば、ビス［４−（ジフェニルスルホニル）フェニル］スルフィドビスヘキサフルオロホスフェート、ビス［４−（ジフェニルスルホニル）フェニル］スルフィドビスヘキサフルオロアンチモネート、ビス［４−（ジフェニルスルホニル）フェニル］スルフィドビステトラフルオロボレート、ビス［４−（ジフェニルスルホニル）フェニル］スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル−４−（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル−４−（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル−４−（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル−４−（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス［４−（ジ（４−（２−ヒドロキシエトキシ））フェニルスルホニル）フェニル］スルフィドビスヘキサフルオロホスフェート、ビス［４−（ジ（４−（２−ヒドロキシエトキシ））フェニルスルホニル）フェニル］スルフィドビスヘキサフルオロアンチモネート、ビス［４−（ジ（４−（２−ヒドロキシエトキシ））フェニルスルホニル）フェニル］スルフィドビステトラフルオロボレート、ビス［４−（ジ（４−（２−ヒドロキシエトキシ））フェニルスルホニル）フェニル］スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４−メチルフェニル−４−（１−メチルエチル）フェニルヨードニウムヘキサフルオロホスフェート、４−メチルフェニル−４−（２−メチルプロピル）フェニルヨードニウムヘキサフルオロホスフェート、４−メチルフェニル−４−（２−メチルプロピル）フェニルヨードニウムヘキサフルオロアンチモネート、４−メチルフェニル−４−（２−メチルプロピル）フェニルヨードニウムテトラフルオロボレート、４−メチルフェニル−４−（２−メチルプロピル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４−メチルフェニル−４−（１−メチルエチル）フェニルヨードニウムヘキサフルオロアンチモネート、４−メチルフェニル−４−（１−メチルエチル）フェニルヨードニウムテトラフルオロボレート、４−メチルフェニル−４−（１−メチルエチル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。これらの市販品としては、例えば、チバガイギー社製イルガキュアー２６１、旭電化工業社製オプトマーＳＰ−１５０、ＳＰ−１５１、ＳＰ−１７０、ＳＰ−１７１、ゼネラルエレクトリック社製ＵＶＥ−１０１４、サートマー社製ＣＤ−１０１２、三新化学工業社製サンエイドＳＩ−４５、ＳＩ−６０Ｌ、ＳＩ−８０Ｌ、ＳＩ−１００Ｌ、日本曹達社製ＣＩ−２０６４、ＣＩ−２６３９、ＣＩ−２６２４、ＣＩ−２４８１、ローヌ・プーラン社製ＲＨＯＤＯＲＳＩＬ ＰＨＯＴＯＩＮＩＴＩＡＴＯＲ２０７４、ユニオンカーバイド社製ＵＶＩ−６９９０、ミドリ化学社製ＢＢＩ−１０３、ＭＰＩ−１０３、ＴＰＳ−１０３、ＭＤＳ−１０３、ＤＴＳ−１０３、ＮＡＴ−１０３、ＮＤＳ−１０３等を用いることが出来る。上記カチオン系硬化剤（Ｃ）は、単独で使用してもよいし２種類以上を組み合わせて使用してもよい。その本発明の樹脂組成物中における含有量は、０．１〜５質量％が好ましい。０．１質量％より少ない場合には硬化が不十分になり、好ましくない。また５質量％より多い場合には、得られる成形品の物性上或いは経済的にも好ましくない。本発明では、紫外線照射により本発明の樹脂組成物を硬化させ成形品を得ることができるが、該樹脂組成物中にフィラー類を一定量以上含む場合は、加熱により硬化させることが好ましい。   Specific examples of the cationic curing agent (C) include, for example, bis [4- (diphenylsulfonyl) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonyl) phenyl] sulfide bishexafluoroantimonate, bis [ 4- (diphenylsulfonyl) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonyl) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenyl) Thio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl] sulfide bishexafluoroantimonate, Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl] sulfide bistetrafluoroborate, bis [4- Di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodoniumtetrakis (pentafluoro) Phenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4 -Methylphenyl-4- (1-methylethyl) phenyliodine Donium hexafluorophosphate, 4-methylphenyl-4- (2-methylpropyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (2-methylpropyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl- 4- (2-methylpropyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (2-methylpropyl) phenyliodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) Phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodine Tetrakis (pentafluorophenyl) borate, and the like. Examples of these commercially available products include Irgacure 261 manufactured by Ciba Geigy, Optomer SP-150, SP-151, SP-170, SP-171 manufactured by Asahi Denka Kogyo Co., Ltd. UVE-1014 manufactured by General Electric Co., CD manufactured by Sartomer Co. -1012, San-Aid SI-45, SI-60L, SI-80L, SI-100L manufactured by Sanshin Chemical Industry Co., Ltd. CI-2064 manufactured by Nippon Soda Co., Ltd., CI-2640, CI-2624, CI-2481, Rhone-Poulenc RHODOLSIL PHOTOINITITOR 2074 manufactured by Union Carbide, UVI-6990 manufactured by Union Carbide, BBI-103 manufactured by Midori Chemical Co., MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103, and the like can be used. The cationic curing agent (C) may be used alone or in combination of two or more. The content in the resin composition of the present invention is preferably 0.1 to 5% by mass. When it is less than 0.1% by mass, curing is insufficient, which is not preferable. Moreover, when more than 5 mass%, it is not preferable also on the physical property of the obtained molded article, or economically. In the present invention, the resin composition of the present invention can be cured by ultraviolet irradiation to obtain a molded product. However, when a certain amount or more of fillers are contained in the resin composition, it is preferably cured by heating.

また、本発明の樹脂組成物には、本発明の効果を損なわない範囲内で、任意の添加剤を併用することができる。添加剤としては、例えば、酸化防止剤、光安定剤、紫外線吸収剤、レベリング剤、粘度調整剤、顔料・有機染料などの着色剤等が例示できる。本発明の樹脂組成物には、一般に知られている不飽和ポリエステル樹脂；ビニルウレタン樹脂；ビニルエステルウレタン樹脂；ポリイソシアネート；ポリエポキシド；アクリル樹脂類；アルキッド樹脂類；尿素樹脂類；メラニン樹脂類；ポリ酢酸ビニル；酢酸ビニル系共重合体；ポリジエン系エラストマー；飽和ポリエステル類；飽和ポリエーテル類；ニトロセルローズ、セルローズアセテートブチレートなどのセルローズ誘導体；アマニ油、桐油、大豆油、ヒマシ油、エポキシ化油等の油脂類ごとき他の慣用の天然および合成高分子化合物を、耐メタノール性および耐熱性を損なわない範囲で添加できる。また、この際、パーオキシラジカル化合物等の所謂、ラジカル系硬化剤を併用することもできる。   Moreover, arbitrary additives can be used together for the resin composition of this invention within the range which does not impair the effect of this invention. Examples of the additives include antioxidants, light stabilizers, ultraviolet absorbers, leveling agents, viscosity modifiers, colorants such as pigments and organic dyes, and the like. The resin composition of the present invention includes generally known unsaturated polyester resins; vinyl urethane resins; vinyl ester urethane resins; polyisocyanates; polyepoxides; acrylic resins; alkyd resins; urea resins; Vinyl acetate; vinyl acetate copolymer; polydiene elastomer; saturated polyesters; saturated polyethers; cellulose derivatives such as nitrocellulose and cellulose acetate butyrate; linseed oil, tung oil, soybean oil, castor oil, epoxidized oil, etc. Other conventional natural and synthetic polymer compounds such as oils and fats can be added as long as the methanol resistance and heat resistance are not impaired. At this time, a so-called radical curing agent such as a peroxy radical compound may be used in combination.

本発明において、前記エポキシ化合物（Ａ）７０〜９９質量部及び前記芳香族系単量体（Ｂ）１〜３０質量部の混合物は、常温（２５℃）において液状であり、２５℃で液状とは、２５℃での粘度が１００ｄＰａ・Ｓ以下であることを言い、０．１〜１００ｄＰａ・Ｓであることが好ましく、より好ましくは０．１〜６０ｄＰａ・Ｓである。１００ｄＰａ・Sを超えると、成形加工の際の含浸性、附型性等の成形加工性が劣り好ましくない。   In the present invention, a mixture of 70 to 99 parts by mass of the epoxy compound (A) and 1 to 30 parts by mass of the aromatic monomer (B) is liquid at room temperature (25 ° C.) and is liquid at 25 ° C. Means that the viscosity at 25 ° C. is 100 dPa · S or less, preferably 0.1 to 100 dPa · S, and more preferably 0.1 to 60 dPa · S. If it exceeds 100 dPa · S, the moldability such as impregnation and moldability during molding is inferior, which is not preferable.

本発明の樹脂組成物は、エポキシ化合物（Ａ）が７０〜９９質量部、芳香族系単量体（Ｂ）が１〜３０質量部、カチオン系硬化剤（Ｃ）が好ましくは０．１〜５質量部含有されていることを特徴とするカチオン重合性樹脂組成物である。耐熱性を保持し、成形加工性が良好となる樹脂組成物の樹脂粘度を、本発明の範囲に調整するためには、上記の特定の配合比率とすることが必要である。   In the resin composition of the present invention, the epoxy compound (A) is 70 to 99 parts by mass, the aromatic monomer (B) is 1 to 30 parts by mass, and the cationic curing agent (C) is preferably 0.1 to A cationically polymerizable resin composition containing 5 parts by mass. In order to adjust the resin viscosity of the resin composition that retains heat resistance and has good molding processability within the range of the present invention, it is necessary to set the specific blending ratio as described above.

本発明の用途においては、本発明の樹脂組成物中は有機および／または無機フィラーを含有することが好ましい。有機および無機フィラーとしては、例えば、炭酸カルシウム、タルク、マイカ、クレー、シリカパウダー、コロイダルシリカ、硫酸バリウム、水酸化アルミニウム、酸化チタン、酸化スズ、ガラス粉、ガラスビーズ、砕砂、カーボンフィラー、カーボンナノチューブ等の無機或いは有機系の充填剤を例示でき、添加するフィラーの特性を成形品に付与できる。即ちこれらフィラー類の添加により、例えば、導電性、接着性、難燃性、放熱性、耐熱性、低収縮性等の各種特性を成形品に付与できる。   In the use of the present invention, the resin composition of the present invention preferably contains an organic and / or inorganic filler. Examples of organic and inorganic fillers include calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, titanium oxide, tin oxide, glass powder, glass beads, crushed sand, carbon filler, and carbon nanotube. Examples of such inorganic or organic fillers can be given, and the properties of the filler to be added can be imparted to the molded product. That is, by adding these fillers, for example, various properties such as conductivity, adhesiveness, flame retardancy, heat dissipation, heat resistance, and low shrinkage can be imparted to the molded article.

また、本発明の樹脂組成物には、ガラス繊維、炭素繊維、有機繊維、金属繊維等を繊維補強材として含有させ、強度を向上させた成形品とすることもできる。   In addition, the resin composition of the present invention can contain a glass fiber, carbon fiber, organic fiber, metal fiber, or the like as a fiber reinforcing material to obtain a molded product with improved strength.

本発明の成形品は、上記本発明の樹脂組成物を硬化せしめて得られる。そして必要に応じて成形すれば良い。樹脂組成物を硬化させる方法としては、高温炉等を用いた加熱硬化や、メタルハライドランプ、水銀ランプ等の一般的な紫外線光照射装置を用いた紫外線照射による硬化が挙げられる。
先に記載したフィラー類を本発明の樹脂組成物に含有させる場合は、加熱硬化させることが好ましい。 The molded product of the present invention can be obtained by curing the resin composition of the present invention. And what is necessary is just to shape | mold as needed. Examples of the method of curing the resin composition include heat curing using a high temperature furnace or the like, and curing by ultraviolet irradiation using a general ultraviolet light irradiation device such as a metal halide lamp or a mercury lamp.
When the above-described fillers are contained in the resin composition of the present invention, it is preferable to heat cure.

本発明の樹脂組成物を硬化させるための加熱温度としては、特に限定されないが、５０℃〜２５０℃の範囲が好ましく、より好ましくは５０℃〜２００℃の範囲である。温度が５０℃より低いと、硬化に時間がかかり成形サイクル上好ましくない。   Although it does not specifically limit as heating temperature for hardening the resin composition of this invention, The range of 50 to 250 degreeC is preferable, More preferably, it is the range of 50 to 200 degreeC. When the temperature is lower than 50 ° C., it takes time for curing, which is not preferable in terms of the molding cycle.

本発明の成形品を得るための成形方法は、特に制限されないが、具体的には、所謂、加熱金型を用いたプレス成形、射出成形、ハンドレイアップ、スプレーアップ成形、ＲＴＭ（レジントランスファーモールディング）成形、連続成形、引き抜き成形等により、硬化物を所望の形状に成形する方法が例示できる。または、ガラス板等で形成した型内に本発明の樹脂組成物を充填して、加熱および成形を同時に行ってもよい。   The molding method for obtaining the molded product of the present invention is not particularly limited. Specifically, so-called press molding using a heating die, injection molding, hand lay-up, spray-up molding, RTM (resin transfer molding). ) A method of forming a cured product into a desired shape by molding, continuous molding, pultrusion molding or the like can be exemplified. Or you may fill the resin composition of this invention in the type | mold formed with the glass plate etc., and perform a heating and shaping | molding simultaneously.

本発明の成形品は、特にその用途は限定されないが、耐アルコール性が要求される用途に好適であり、具体的には、アルコール類が単独でまたはアルコール類が一部含有されている化合物が常時又は一時的に接触しうる部材として使用するのに好適である。このようなものとして、例えば、大型容器、小型容器、タンク槽、パネル、自動車部材、電気電子部材、平板、波板、フィルム、シート、封止材等が挙げられるが、特にこれらに限定するものではない。   The use of the molded article of the present invention is not particularly limited, but it is suitable for applications requiring alcohol resistance. Specifically, a compound containing alcohol alone or a part of alcohol is contained. It is suitable for use as a member that can be contacted constantly or temporarily. Examples of such include, but are not limited to, large containers, small containers, tank tanks, panels, automobile members, electric and electronic members, flat plates, corrugated sheets, films, sheets, sealing materials, and the like. is not.

以下本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また文章中「部」とあるのは、質量部を示すものである。   EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “part” in the text indicates mass part.

（実施例１）
ビスフェノールＦ型エポキシ化合物としてエピクロン８３０（大日本インキ化学工業株式会社製、エポキシ当量１７０〜１９０ｇ／ｅｑ.）９０部、ジビニルベンゼン（新日鉄化学社製）１０部を均一混合した。得られた混合物の粘度は、６．５ｄＰａ・ｓ（２５℃）であり、ＪＩＳ−Ｋ−６９１９に準じ２５℃で測定した。粘度の測定方法は以下の実施例及び比較例でも同様である。
これに、予め少量のアセトンで希釈したカチオン系硬化剤サンエードＳＩ−４５（三新化学社製）を１部加え良く攪拌した後、得られた樹脂組成物を、減圧脱泡処理を行い気泡が入らない様にして、下記評価方法に記載のガラス板から作成した型内へ流し込み、６０℃の乾燥機に１時間入れ、１２０℃へ昇温して１時間保持し、更に１５０℃へ昇温し、１時間保持、硬化させ、冷却後、ガラス板から硬化物成形品を剥がし、下記記載の評価方法に従い、評価用試験片を規定の大きさに切り出し、耐アルコール性および各特性評価を行った。 (Example 1)
As a bisphenol F type epoxy compound, 90 parts of Epicron 830 (manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 170-190 g / eq.) And 10 parts of divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd.) were uniformly mixed. The viscosity of the obtained mixture was 6.5 dPa · s (25 ° C.), and was measured at 25 ° C. according to JIS-K-6919. The viscosity measurement method is the same in the following examples and comparative examples.
After adding 1 part of a cationic curing agent Sanade SI-45 (manufactured by Sanshin Chemical Co., Ltd.) diluted in advance with a small amount of acetone and stirring well, the obtained resin composition was subjected to vacuum defoaming treatment to remove bubbles. Pour into a mold made from the glass plate described in the evaluation method below, put in a dryer at 60 ° C for 1 hour, raise to 120 ° C, hold for 1 hour, and further raise to 150 ° C Hold for 1 hour, cure, cool, peel off the cured product from the glass plate, cut out the test specimen for evaluation according to the evaluation method described below, and evaluate the alcohol resistance and each characteristic. It was.

（実施例２）
ノボラック型エポキシ化合物としてエピクロン７４０（大日本インキ化学工業株式会社製、エポキシ当量１７０〜１９０ｇ／ｅｑ.）８０部、ジビニルベンゼン（新日鉄化学社製）２０部を混合攪拌した。得られた混合物の粘度は、４０ｄＰａ・ｓ（２５℃）であった。
これに、予め少量のアセトンで希釈したカチオン系硬化剤サンエードＳＩ−４５（三新化学社製）を１部加え良く攪拌し、得られた樹脂組成物を実施例１と同様にして硬化させ、評価用試験片を切り出し、耐アルコール性および各特性評価を行った。 (Example 2)
As a novolak type epoxy compound, 80 parts of Epicron 740 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 170-190 g / eq.) And 20 parts of divinylbenzene (Nippon Steel Chemical Co., Ltd.) were mixed and stirred. The viscosity of the obtained mixture was 40 dPa · s (25 ° C.).
To this, 1 part of a cationic curing agent Sanade SI-45 (manufactured by Sanshin Chemical Co., Ltd.) diluted in advance with a small amount of acetone was added and stirred well, and the resulting resin composition was cured in the same manner as in Example 1. A test specimen for evaluation was cut out and evaluated for alcohol resistance and characteristics.

（実施例３）
エポキシ化合物としてエピクロン８３０（大日本インキ化学工業株式会社製）９０部、スチレン１０部を混合攪拌した。得られた混合物の粘度は、４．１ｄＰａ・ｓ（２５℃）であった。
これに、カチオン系硬化剤サンエードＳＩ−１００Ｌ（三新化学社製）を１．６部加え良く攪拌した後、得られた樹脂組成物を、減圧脱泡処理を行い気泡が入らない様にして、下記評価方法に記載のガラス板から作成した型内へ流し込み、１２０℃の乾燥機に１時間入れ、１５０℃へ昇温して１時間保持し、更に１８０℃へ昇温して１時間保持し、完全硬化させ、冷却後、ガラス板から硬化物成形品を剥がし、下記記載の評価方法に従い、評価用試験片を規定の大きさに切り出し、耐アルコール性および各種特性評価を行った。 (Example 3)
As an epoxy compound, 90 parts of Epicron 830 (manufactured by Dainippon Ink and Chemicals) and 10 parts of styrene were mixed and stirred. The viscosity of the obtained mixture was 4.1 dPa · s (25 ° C.).
To this, 1.6 parts of cationic curing agent Sanade SI-100L (manufactured by Sanshin Chemical Co., Ltd.) was added and stirred well, and the resulting resin composition was subjected to vacuum defoaming treatment to prevent bubbles from entering. Pour into a mold made from the glass plate described in the following evaluation method, put in a dryer at 120 ° C. for 1 hour, raise to 150 ° C. and hold for 1 hour, further raise to 180 ° C. and hold for 1 hour The cured product was peeled off from the glass plate after complete curing, and the test specimen for evaluation was cut into a prescribed size according to the evaluation method described below, and the alcohol resistance and various characteristics were evaluated.

（比較例１）
既存の熱硬化性樹脂組成物である不飽和ポリエステル樹脂の代表としてイソフタル酸系不飽和ポリエステル樹脂サンドーマＦＧ−２８３（ディーエイチ・マテリアル株式会社製、樹脂粘度４．５ｄＰａ・ｓ（２５℃））１００部を用いた。
これに、促進剤６％ナフテン酸コバルトを０．２部加え均一に混合し、硬化剤としてメチルエチルケトンパーオキサイド（パーメックＮ、日本油脂社製）１．０部を加え、混合攪拌し、樹脂を調製した。
次いで、下記評価方法に従い、該樹脂を型内へ流し込み、常温にて硬化後、１２０℃乾燥機中にて２時間硬化させ、評価用試験片を作成し、下記評価方法に従い、耐アルコール性および各特性の評価を行った。 (Comparative Example 1)
As a representative of unsaturated polyester resin which is an existing thermosetting resin composition, isophthalic acid unsaturated polyester resin Sandoma FG-283 (manufactured by DH Material Co., Ltd., resin viscosity 4.5 dPa · s (25 ° C.)) 100 Parts were used.
To this, 0.2 part of accelerator 6% cobalt naphthenate was added and mixed uniformly, 1.0 part of methyl ethyl ketone peroxide (Permec N, manufactured by NOF Corporation) was added as a curing agent, and mixed and stirred to prepare a resin. did.
Then, according to the following evaluation method, the resin is poured into a mold, cured at room temperature, and then cured in a 120 ° C. dryer for 2 hours to prepare a test piece for evaluation. Each characteristic was evaluated.

（比較例２）
既存の熱硬化性樹脂組成物であるビニルエステル樹脂の代表としてエクスドーマＴＰ−８３５（ディーエイチ・マテリアル株式会社製、樹脂粘度４．８ｄＰａ・ｓ（２５℃））１００部を用いた。
これに、促進剤６％ナフテン酸コバルトを０．２部加え均一に混合し、硬化剤としてメチルエチルケトンパーオキサイド（パーメックＮ、日本油脂社製）１．０部を加え、混合攪拌し、樹脂を調製した。次いで、比較例１と同様に評価用試験片をを作成し、耐アルコール性評価および各特性評価を行った。 (Comparative Example 2)
As a representative vinyl ester resin that is an existing thermosetting resin composition, 100 parts of Exdoma TP-835 (manufactured by DH Material Co., Ltd., resin viscosity 4.8 dPa · s (25 ° C.)) was used.
To this, 0.2 part of accelerator 6% cobalt naphthenate was added and mixed uniformly, 1.0 part of methyl ethyl ketone peroxide (Permec N, manufactured by NOF Corporation) was added as a curing agent, and mixed and stirred to prepare a resin. did. Subsequently, the test piece for evaluation was created similarly to the comparative example 1, and alcohol resistance evaluation and each characteristic evaluation were performed.

（比較例３）
本発明で用いる芳香族系単量体（Ｂ）を含有しない例として、エポキシ化合物としてエピクロン７４０（大日本インキ化学工業株式会社製）を用いようとしたが、常温での該エポキシ化合物の粘度が１００ｄＰａ・ｓより大きく粘調で、実施例１と同様にカチオン系硬化剤を添加し、評価用試験片を作成しようとしたが、高粘度のためガラス板から作成した型内へ樹脂を流し込むことができず、よって評価用成形品を作成することができず、耐アルコール性等の評価をおこなうことができなかった。 (Comparative Example 3)
As an example that does not contain the aromatic monomer (B) used in the present invention, it was attempted to use Epicron 740 (manufactured by Dainippon Ink & Chemicals, Inc.) as an epoxy compound, but the viscosity of the epoxy compound at room temperature was The viscosity was greater than 100 dPa · s, and a cationic curing agent was added in the same manner as in Example 1 to create a test piece for evaluation. However, due to the high viscosity, the resin was poured into a mold created from a glass plate. Therefore, a molded article for evaluation could not be produced, and the alcohol resistance and the like could not be evaluated.

（比較例４）
エポキシ化合物として芳香族系骨格を有さない脂肪族系エポキシ化合物であるセロキサイド２０２１Ｐ（ダイセル化学社製、樹脂粘度２．８ｄＰａ・ｓ（２５℃））１００部を用いた。
これに、カチオン系硬化剤サンエードＳＩ−１００Ｌ（三新化学社製）を１．６部加え、得られた樹脂組成物を、減圧脱泡処理を行い気泡が入らない様にして、下記評価方法に記載のガラス板から作成した型内へ流し込み、１２０℃の乾燥機に１時間入れ、１５０℃へ昇温して１時間保持し、更に１８０℃へ昇温して１時間保持し、完全硬化させ、冷却後、ガラス板から硬化物成形品を剥がし、下記記載の評価方法に従い、評価用試験片を規定の大きさに切り出し、耐アルコール性および各特性の評価を行った。しかしながら、耐アルコール性試験後の試験片は、メタノールにより腐食が甚だしく、元の形状を保持していない状態であったため、重量変化率およびバーコール硬度の評価はできなかった。 (Comparative Example 4)
As the epoxy compound, 100 parts of Celoxide 2021P (Daicel Chemical Industries, resin viscosity 2.8 dPa · s (25 ° C.)), which is an aliphatic epoxy compound having no aromatic skeleton, was used.
To this, 1.6 parts of cationic curing agent Sanade SI-100L (manufactured by Sanshin Chemical Co., Ltd.) was added, and the resulting resin composition was subjected to vacuum defoaming treatment to prevent bubbles from entering. Pour into a mold made from the glass plate described in 1), put in a dryer at 120 ° C for 1 hour, raise to 150 ° C and hold for 1 hour, further raise to 180 ° C and hold for 1 hour, complete curing After cooling, the cured product was peeled off from the glass plate, and according to the evaluation method described below, the test piece for evaluation was cut out to a specified size, and the alcohol resistance and each characteristic were evaluated. However, the test piece after the alcohol resistance test was severely corroded by methanol and did not retain its original shape, and thus the weight change rate and the Barcol hardness could not be evaluated.

（比較例５）
エポキシ化合物としてエピクロン８３０（大日本インキ化学工業株式会社製）９０部、実施例３で用いた芳香族系単量体であるスチレンの代わりに、脂肪族系単量体であるノルマルブチルビニルエーテルを１０部用い、実施例３と同様に混合攪拌した。得られた混合物の粘度は、３．９ｄＰａ・ｓ（２５℃）であった。
これに、カチオン系硬化剤サンエードＳＩ−１００Ｌ（三新化学社製）を１．６部加え良く攪拌した後、得られた樹脂組成物を、減圧脱泡処理を行い気泡が入らない様にして、下記評価方法に記載のガラス板から作成した型内へ流し込み、１２０℃の乾燥機に１時間入れ、１５０℃へ昇温して１時間保持し、更に１８０℃へ昇温して１時間保持し、完全硬化させ、冷却後、ガラス板から硬化物成形品を剥がした。しかし得られた硬化物は、茶白濁しており、脆く、硬化物のバーコール硬度計では、硬度を示さず成形品としての評価はできなかった。 (Comparative Example 5)
As an epoxy compound, 90 parts of Epicron 830 (manufactured by Dainippon Ink & Chemicals, Inc.) and 10 of normal butyl vinyl ether which is an aliphatic monomer instead of styrene which is an aromatic monomer used in Example 3 The mixture was mixed and stirred in the same manner as in Example 3. The viscosity of the obtained mixture was 3.9 dPa · s (25 ° C.).
To this, 1.6 parts of cationic curing agent Sanade SI-100L (manufactured by Sanshin Chemical Co., Ltd.) was added and stirred well, and the resulting resin composition was subjected to vacuum defoaming treatment to prevent bubbles from entering. Pour into a mold made from the glass plate described in the following evaluation method, put in a dryer at 120 ° C. for 1 hour, raise to 150 ° C. and hold for 1 hour, further raise to 180 ° C. and hold for 1 hour The cured product was peeled off from the glass plate after being completely cured and cooled. However, the obtained cured product was brown and turbid and brittle, and the cured product's Barcol hardness tester did not show hardness and could not be evaluated as a molded product.

（試験片の作成方法、評価方法）
＜評価用試験片の作成＞
３０ｃｍ×３０ｃｍ大の２枚のガラス板に離型剤を塗布し、塩化ビニル樹脂製チューブをガラス板の間に挟み、スペーサーを用い隙間３ｍｍとなる様調整し、実施例、比較例で示された各樹脂組成物を流し込み、各条件にて硬化させ、冷却後、ガラスを外して、平滑な厚さ３ｍｍの成形品を得た。得られた成形品を、８．３ｃｍ×３ｃｍ大に切削し、評価用試験片とした。
＜耐アルコール性評価＞
アルコール類において浸透、腐食性の強いメタノールを用い、メタノールと蒸留水の９０質量部／１０質量部の比率からなる溶液を調製し、このアルコール水溶液をステンレス製耐圧オートクレーブに入れ、各評価用試験片を投入、密閉し、そのオートクレーブを６０℃の乾燥機中に静置し、３００時間後、試験片を取り出し、メタノール水溶液を素早く拭き取り、常温での試験片の外観変化を観察し、また重量変化率およびバーコール硬度変化を測定した。重量変化率は、乾燥機から取り出した後の試験片重量を、乾燥機投入前の試験片重量で除した値から算出した。また、バーコール硬度は、ＪＩＳ−Ｋ−７０６０、ＧＹＺＪ９３４−１に準じて評価した。重量変化率は、５．０％以下を○、それ以上を×とし、バーコール硬度は、２０以上の値を保持している場合を○、それ以下を×として評価を行った。結果を表１及び２に示す。
＜外観観察＞
耐アルコール性評価後の前記試験片について、クラックの有無、膨れ膨潤の有無を観察した。結果を表１及び２に示す。
＜耐熱性評価＞
ＪＩＳ−Ｋ−７２０７に準じ成形品から試験片を作成し、試験片の熱変形温度を測定し、１００℃以上を耐熱性の有無の目安として判断した。結果を表１及び２に示す。 (Test specimen preparation and evaluation methods)
<Creation of test specimen for evaluation>
A release agent is applied to two glass plates of 30 cm × 30 cm, a vinyl chloride resin tube is sandwiched between the glass plates, and a gap is adjusted to 3 mm using a spacer, and each of the examples and comparative examples shown in the examples. The resin composition was poured and cured under each condition, and after cooling, the glass was removed to obtain a smooth molded product having a thickness of 3 mm. The obtained molded product was cut into a size of 8.3 cm × 3 cm to obtain a test piece for evaluation.
<Evaluation of alcohol resistance>
Using methanol which is highly osmotic and corrosive in alcohols, a solution having a ratio of 90 parts by mass to 10 parts by mass of methanol and distilled water is prepared. This alcohol aqueous solution is put in a stainless steel pressure-resistant autoclave, and each test piece for evaluation The autoclave is allowed to stand in a dryer at 60 ° C., and after 300 hours, the test piece is taken out, the methanol aqueous solution is quickly wiped off, the appearance change of the test piece at normal temperature is observed, and the weight is changed. The rate and the change in barcol hardness were measured. The weight change rate was calculated from a value obtained by dividing the weight of the test piece after being taken out from the dryer by the weight of the test piece before being put into the dryer. Further, the Barcol hardness was evaluated according to JIS-K-7060 and GYZJ934-1. The weight change rate was evaluated as ○ when 5.0% or less, and × when it was higher, and when the Barcol hardness was holding a value of 20 or higher as ○ and when it was less than ×. The results are shown in Tables 1 and 2.
<Appearance observation>
The test piece after the alcohol resistance evaluation was observed for the presence or absence of cracks and the presence or absence of swelling and swelling. The results are shown in Tables 1 and 2.
<Heat resistance evaluation>
A test piece was prepared from the molded product according to JIS-K-7207, the heat distortion temperature of the test piece was measured, and 100 ° C. or higher was judged as a measure of the presence or absence of heat resistance. The results are shown in Tables 1 and 2.

Figure 2008163068
Figure 2008163068

Figure 2008163068
Figure 2008163068

Claims (5)

エポキシ基を２〜４個含有しかつ芳香族系骨格を有するエポキシ化合物（Ａ）７０〜９９質量部、ビニル基を１〜２個有する芳香族系単量体（Ｂ）１〜３０質量部及びカチオン系硬化剤（Ｃ）を含有し、前記エポキシ化合物（Ａ）及び前記芳香族系単量体（Ｂ）の前記質量比における混合物が常温（２５℃）で液状であることを特徴とする成形品用カチオン重合性樹脂組成物。   70 to 99 parts by mass of an epoxy compound (A) containing 2 to 4 epoxy groups and having an aromatic skeleton, 1 to 30 parts by mass of an aromatic monomer (B) having 1 to 2 vinyl groups, and A molding comprising a cationic curing agent (C), wherein the mixture of the epoxy compound (A) and the aromatic monomer (B) in the mass ratio is liquid at normal temperature (25 ° C.). Product cationically polymerizable resin composition. 前記芳香族系単量体（Ｂ）が、ジビニルベンゼン及びスチレンから選ばれる一種以上である請求項１に記載の成形品用カチオン重合性樹脂組成物。   The cationically polymerizable resin composition for molded articles according to claim 1, wherein the aromatic monomer (B) is at least one selected from divinylbenzene and styrene. 前記エポキシ化合物（Ａ）が、ビスフェノール型エポキシ化合物である請求項１に記載の成形品用カチオン重合性樹脂組成物。   The cationically polymerizable resin composition for molded articles according to claim 1, wherein the epoxy compound (A) is a bisphenol type epoxy compound. 常温（２５℃）での前記エポキシ化合物（Ａ）及び前記芳香族系単量体（Ｂ）の前記質量比における混合物の粘度が、０．１ 〜６０ｄＰａ・ｓの範囲である請求項１に記載の成形品用カチオン重合性樹脂組成物。   The viscosity of the mixture at the mass ratio of the epoxy compound (A) and the aromatic monomer (B) at room temperature (25 ° C) is in the range of 0.1 to 60 dPa · s. A cationically polymerizable resin composition for molded articles. 請求項１〜４のいずれか一項に記載の成形品用カチオン重合性樹脂組成物を硬化せしめて得られることを特徴とする成形品。   A molded product obtained by curing the cationically polymerizable resin composition for molded products according to any one of claims 1 to 4.
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JP2540846B2 (en) * 1987-03-14 1996-10-09 ソニー株式会社 Solder resistant protection material
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CN104718233A (en) * 2012-10-15 2015-06-17 株式会社大赛璐 Curable resin composition, and cured product thereof
JPWO2014061648A1 (en) * 2012-10-15 2016-09-05 株式会社ダイセル Curable resin composition and cured product thereof
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