JP4585843B2 - Triazine compound - Google Patents
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- JP4585843B2 JP4585843B2 JP2004361056A JP2004361056A JP4585843B2 JP 4585843 B2 JP4585843 B2 JP 4585843B2 JP 2004361056 A JP2004361056 A JP 2004361056A JP 2004361056 A JP2004361056 A JP 2004361056A JP 4585843 B2 JP4585843 B2 JP 4585843B2
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Description
本発明は、化１で示される新規なトリアジン化合物に関するものである。 The present invention relates to a novel triazine compound represented by Chemical Formula 1.
エポキシ樹脂は、機械的強度ならびに電気的絶縁特性に優れ、また接着性、耐水性、耐熱性等が良好であるところから、構造用複合材料、土木建築用材料を始めとして、電気・電子材料分野における絶縁被覆材や接着剤、ＬＳＩや発光ダイオード用の封止剤、プリント配線基盤用のインク、塗料、積層板等の原料として広く使用されている。
上記に例示される用途に対しては、各々異なった特性が求められるが、耐熱性、耐候性および透明性を改善する手段として、エポキシ樹脂を基材としてトリグリシジルイソシアヌレート（以下、ＴＧＩＣという）を配合したエポキシ樹脂組成物が提案されている。
Epoxy resins are excellent in mechanical strength and electrical insulation properties, and have good adhesion, water resistance, heat resistance, etc., and are used in structural and materials for civil engineering and construction, as well as electrical and electronic materials. Are widely used as raw materials for insulating coating materials and adhesives, sealing agents for LSIs and light emitting diodes, inks for printed wiring boards, paints, laminates and the like.
For the applications exemplified above, different properties are required, but as a means of improving heat resistance, weather resistance and transparency, triglycidyl isocyanurate (hereinafter referred to as TGIC) using epoxy resin as a base material. There has been proposed an epoxy resin composition containing the above.
このＴＧＩＣは、化３の構造式に示されるように、トリアジン環を骨格として、１分子中に３つのグリシジル基を有するので、基材となるエポキシ樹脂に添加して用いる場合には、３次元架橋剤として作用し、エポキシ樹脂の耐熱性、耐候性、透明性を向上させることができる。 Since this TGIC has a triazine ring as a skeleton and has three glycidyl groups in one molecule as shown in the structural formula of Chemical Formula 3, when used by adding to an epoxy resin as a base material, It acts as a crosslinking agent and can improve the heat resistance, weather resistance and transparency of the epoxy resin.
しかしながらＴＧＩＣは結晶性が高い固体化合物であるため、有機溶剤や樹脂に対する溶解性が低く、ＴＧＩＣとエポキシ樹脂を加熱混合して液状の均一な組成物とし、更には該組成物を有機溶剤に溶かしてワニスとした場合であっても、室温で放置しておくと、ＴＧＩＣの結晶が析出するという問題があった。 However, since TGIC is a solid compound with high crystallinity, its solubility in organic solvents and resins is low, and TGIC and epoxy resin are heated and mixed to form a uniform liquid composition. Further, the composition is dissolved in an organic solvent. Even when the varnish is used, there is a problem that TGIC crystals precipitate when left at room temperature.
このような問題点に対して、特許文献１には、ＴＧＩＣと１個以上の水酸基または１個以上のカルボキシル基を有する化合物との反応生成物が、また特許文献２には、有機溶剤に溶け易い化合物として、ＴＧＩＣとビスフェノールＡまたはテトラブロモビスフェノールＡとの反応生成物が提案されている。 In order to solve such a problem, Patent Document 1 discloses a reaction product of TGIC and one or more hydroxyl groups or compounds having one or more carboxyl groups, and Patent Document 2 dissolves in an organic solvent. As an easy compound, a reaction product of TGIC and bisphenol A or tetrabromobisphenol A has been proposed.
本発明は、エポキシ樹脂との相溶性に優れ、且つエポキシ樹脂の耐熱性、耐候性、透明性等を向上させることができるエポキシ樹脂用添加剤を提供することを目的とする。 An object of this invention is to provide the additive for epoxy resins which is excellent in compatibility with an epoxy resin, and can improve the heat resistance of a epoxy resin, a weather resistance, transparency, etc.
本発明は、化１に示されるトリアジン化合物であり、化４に示されるイソシアヌル酸と化５に示される水添ビスフェノールＡ型エポキシ樹脂とを反応させることにより得られる。 The present invention is a triazine compound represented by Chemical Formula 1 and is obtained by reacting an isocyanuric acid represented by Chemical Formula 4 with a hydrogenated bisphenol A type epoxy resin represented by Chemical Formula 5.
本発明のトリアジン化合物は、構造用複合材料、土木建築用材料を始めとして、電気・電子材料分野における絶縁被覆材や接着剤、ＬＳＩや発光ダイオード用の封止剤、プリント配線基盤用のインク、塗料、積層板等の原料として有用なものであり、基材となるエポキシ樹脂との相溶性に優れ、且つエポキシ樹脂の耐熱性、耐候性、透明性等を向上させることができる。 The triazine compound of the present invention includes structural composite materials, civil engineering and building materials, insulating coating materials and adhesives in the field of electrical and electronic materials, sealing agents for LSIs and light emitting diodes, inks for printed wiring boards, It is useful as a raw material for paints, laminates and the like, has excellent compatibility with the epoxy resin as the base material, and can improve the heat resistance, weather resistance, transparency, etc. of the epoxy resin.
本発明のトリアジン化合物と配合し得るエポキシ樹脂の例としては、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、３、３’，５，５’−テトラメチル−４、４’−ビフェノール型エポキシ樹脂又は４、４’−ビフェノール型エポキシ樹脂のようなビフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂、トリスフェニロールメタン型エポキシ樹脂、テトラキスフェニロールエタン型エポキシ樹脂、及びフェノールジシクロペンタジエンノボラック型エポキシ樹脂等の芳香族エポキシ樹脂やオレフィンを過酸酸化して得られる脂環式エポキシ樹脂等および、これらを水添（水素化）したエポキシ樹脂が挙げられる。 Examples of the epoxy resin that can be blended with the triazine compound of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin. Or biphenol type epoxy resin such as 4,4′-biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin Aromatic epoxy resins such as tetrakisphenylolethane type epoxy resin and phenol dicyclopentadiene novolac type epoxy resin, alicyclic epoxy resins obtained by peracid oxidation of olefins, etc., and hydrogenation (hydrogenation) Mentioned epoxy resin.
本発明のトリアジン化合物は、イソシアヌル酸と水添ビスフェノールＡ型エポキシ樹脂とをリン系、アミン系等の触媒存在下、溶媒中で加熱反応させることにより得られる。 The triazine compound of the present invention can be obtained by heat-reacting isocyanuric acid and hydrogenated bisphenol A type epoxy resin in a solvent in the presence of a phosphorus-based or amine-based catalyst.
本発明の実施において使用される水添ビスフェノールＡ型エポキシ樹脂は、化５の一般式で示されるものであり、工業用薬品として入手できるものとして例えば、ジャパンエポキシレジン社製のＹＸ８０００、ＹＸ８０３４等が挙げられる。 The hydrogenated bisphenol A type epoxy resin used in the practice of the present invention is represented by the general formula of Chemical Formula 5, and examples of those that can be obtained as industrial chemicals include YX8000 and YX8034 manufactured by Japan Epoxy Resins. Can be mentioned.
前記の反応において、水添ビスフェノールＡ型エポキシ樹脂の使用量は、イソシアヌル酸に対して、３〜８倍モルが好ましく、３〜６倍モルがより好ましい。この使用量が３倍より少ない場合は、生成物であるトリアジン化合物の収率が低下し、８倍より多い場合には、副反応が進行し好ましくない。 In said reaction, the usage-amount of hydrogenated bisphenol A type epoxy resin has preferable 3-8 times mole with respect to isocyanuric acid, and its 3-6 times mole is more preferable. When the amount used is less than 3 times, the yield of the triazine compound as a product is lowered, and when it is more than 8 times, side reactions proceed, which is not preferable.
本発明の実施において使用される触媒としては、リン系ではトリフェニルホスフィン、テトラフェニルホスホニウムブロミド等が、アミン系ではトリエチルアミン、ベンジルジメチルアミン、ベンジルトリメチルアンモニウムクロリド等が挙げられる。なお、触媒の使用量は、水添ビスフェノールＡ型エポキシ樹脂に対して、０．０１〜０．５０倍モルが好ましい。 Examples of the catalyst used in the practice of the present invention include triphenylphosphine and tetraphenylphosphonium bromide for phosphorus systems, and triethylamine, benzyldimethylamine, benzyltrimethylammonium chloride and the like for amine systems. In addition, the usage-amount of a catalyst has preferable 0.01-0.50 times mole with respect to hydrogenated bisphenol A type epoxy resin.
本発明の実施において使用される溶媒としては、トルエン、キシレン、モノクロルベンゼン、ジオキサン等の無極性溶媒、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン等の極性溶媒が挙げられるが、イソシアヌル酸の溶解度が高い点において、極性溶媒が好ましい。 Examples of the solvent used in the practice of the present invention include nonpolar solvents such as toluene, xylene, monochlorobenzene and dioxane, and polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone, but isocyanuric acid. From the viewpoint of high solubility, a polar solvent is preferred.
反応は常圧下で行えばよく、反応温度は６０〜１５０℃が好ましく、反応時間は１〜１０時間が好ましい。 The reaction may be performed under normal pressure, the reaction temperature is preferably 60 to 150 ° C., and the reaction time is preferably 1 to 10 hours.
反応終了後、溶媒を留去して生成物を得ることができるが、必要に応じて適宜の方法により、精製してもよい。 After completion of the reaction, the solvent can be distilled off to obtain the product, but it may be purified by an appropriate method as necessary.
以下、本発明を実施例によって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。
なお、実施例で使用した主原料は次のとおりである。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The main raw materials used in the examples are as follows.
［原料］
・イソシアヌル酸（四国化成工業社製）
・水添ビスフェノールＡ型エポキシ樹脂（ＹＸ−８０００、ＪＥＲ社製、エポキシ当量：２０５ｇ／当量）
・トリフェニルホスフィン（和光純薬工業社製、試薬）
・ジメチルホルムアミド（和光純薬工業社製、試薬）
・シクロヘキサン（和光純薬工業社製、試薬）
[material]
・ Isocyanuric acid (manufactured by Shikoku Chemicals)
-Hydrogenated bisphenol A type epoxy resin (YX-8000, manufactured by JER, epoxy equivalent: 205 g / equivalent)
・ Triphenylphosphine (Wako Pure Chemical Industries, Reagent)
・ Dimethylformamide (Wako Pure Chemical Industries, Reagent)
・ Cyclohexane (manufactured by Wako Pure Chemical Industries, reagent)
〔実施例１〕
＜トリアジン化合物の合成＞
イソシアヌル酸１６．１４ｇ（０．１２５ｍｏｌ）、水添ビスフェノールＡ型エポキシ樹脂３０３．００ｇ（０．７５０ｍｏｌ）を１６１．４０ｇのジメチルホルムアミドに入れ、次いでトリフェニルホスフィン２．１０ｇ（０．００８ｍｏｌ）を加えて撹拌しながら１００℃で３時間加熱反応を行った。続いて、ジメチルホルムアミドを減圧留去し、得られた生成物をシクロヘキサン１２８２．５６ｇで洗浄し、シクロヘキサン不溶物として淡黄色液状物１２６．４３ｇ（０．１０７ｍｏｌ、収率８５．６％）を得た。
[Example 1]
<Synthesis of triazine compound>
Add 16.14 g (0.125 mol) of isocyanuric acid and 303.00 g (0.750 mol) of hydrogenated bisphenol A type epoxy resin to 161.40 g of dimethylformamide, and then add 2.10 g (0.008 mol) of triphenylphosphine. The reaction was conducted at 100 ° C. for 3 hours with stirring. Subsequently, dimethylformamide was distilled off under reduced pressure, and the resulting product was washed with 1282.56 g of cyclohexane to obtain 126.43 g (0.107 mol, yield 85.6%) of a pale yellow liquid as a cyclohexane insoluble matter. It was.
上記液状物のＮＭＲ及びマススペクトルを測定したところ、得られたデータは以下のとおりであった。
・MS(FAB+)m/z：1187(M+)
・NMR(CDCl3)：δ0.72(s,18H),0.92〜1.43(m,54H),1.60〜1.77(m,3H),1.77〜2.15(m,6H)，2.57〜2.74(m,6H),2.78〜2.88(m,3H),3.13〜3.75(m,21H)
・IR(KBr,cm-1)：765,848,908,1014,1092,1253,1370,1465,1510,1695,2864,2940,3320
これらのスペクトルデータから、得られた液状物は、化６で示されるトリアジン化合物であるものと同定した。
When the NMR and mass spectrum of the liquid were measured, the obtained data was as follows.
・ MS (FAB +) m / z: 1187 (M +)
NMR (CDCl 3 ): δ 0.72 (s, 18H), 0.92 to 1.43 (m, 54H), 1.60 to 1.77 (m, 3H), 1.77 to 2.15 (m, 6H), 2.57 to 2.74 (m, 6H) ), 2.78 to 2.88 (m, 3H), 3.13 to 3.75 (m, 21H)
IR (KBr, cm -1 ): 765,848,908,1014,1092,1253,1370,1465,1510,1695,2864,2940,3320
From these spectrum data, the obtained liquid substance was identified as a triazine compound represented by Chemical Formula 6.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004361056A JP4585843B2 (en) | 2004-12-14 | 2004-12-14 | Triazine compound |
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| JP2004361056A JP4585843B2 (en) | 2004-12-14 | 2004-12-14 | Triazine compound |
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| JP2006169141A JP2006169141A (en) | 2006-06-29 |
| JP4585843B2 true JP4585843B2 (en) | 2010-11-24 |
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| JP2004361056A Active JP4585843B2 (en) | 2004-12-14 | 2004-12-14 | Triazine compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009256448A (en) * | 2008-04-16 | 2009-11-05 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition, and cured product thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225641A (en) * | 1988-03-07 | 1989-09-08 | Hitachi Chem Co Ltd | Production of heat-resistant epoxy resin laminate |
| JP2001011057A (en) * | 1999-06-30 | 2001-01-16 | Shikoku Chem Corp | Novel carboxylic acid bearing isocyanuric acid ring and its production and resin composition containing the same |
| WO2003087186A1 (en) * | 2002-03-29 | 2003-10-23 | Taiyo Ink Manufacturing Co., Ltd. | Unsaturated polybranched compounds, curable compositions containing the same and cured articles thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225641A (en) * | 1988-03-07 | 1989-09-08 | Hitachi Chem Co Ltd | Production of heat-resistant epoxy resin laminate |
| JP2001011057A (en) * | 1999-06-30 | 2001-01-16 | Shikoku Chem Corp | Novel carboxylic acid bearing isocyanuric acid ring and its production and resin composition containing the same |
| WO2003087186A1 (en) * | 2002-03-29 | 2003-10-23 | Taiyo Ink Manufacturing Co., Ltd. | Unsaturated polybranched compounds, curable compositions containing the same and cured articles thereof |
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| JP2006169141A (en) | 2006-06-29 |
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