JP2015007165A - Thermosetting composition - Google Patents
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Description
本発明は、熱硬化性組成物に関する。 The present invention relates to a thermosetting composition.
一般的に、熱硬化性組成物にはエポキシ樹脂や硬化剤等が含まれている。熱硬化性組成物から得られる樹脂硬化物は、優れた耐熱性を示すため、ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ：発光ダイオード）を収納するためのパッケージ材料に代表される様々な分野で用いられている。 Generally, an epoxy resin, a curing agent, and the like are included in the thermosetting composition. The cured resin obtained from the thermosetting composition is used in various fields typified by package materials for housing LEDs (Light Emitting Diodes) in order to exhibit excellent heat resistance.
特許文献１では、エポキシ樹脂、硬化剤、及び硬化触媒等を混合し熱硬化性組成物が得られることを開示している。しかしながら、例えば実施例で例示されているエポキシ樹脂として１，３，５−トリス（２，３−エポキシプロピル）−１，３，５−トリアジン−２，４，６−トリオン、硬化剤としてヘキサヒドロ無水フタル酸、硬化触媒としてテトラ−ｎ−ブチルスルホニウム−ｏ，ｏ−ジエチルホスホロジチオエートを用いた場合、それらから作製した熱硬化性組成物が２５℃程度の常温で貯蔵した際に、徐々に硬化反応が進行するという問題があった。すなわち、貯蔵安定性を改善する必要がある。 Patent Document 1 discloses that a thermosetting composition can be obtained by mixing an epoxy resin, a curing agent, a curing catalyst, and the like. However, for example, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione as an epoxy resin exemplified in the examples, hexahydroanhydride as a curing agent When tetra-n-butylsulfonium-o, o-diethylphosphorodithioate is used as a phthalic acid and a curing catalyst, when the thermosetting composition prepared therefrom is stored at room temperature of about 25 ° C., There was a problem that the curing reaction proceeded. That is, it is necessary to improve storage stability.
特許文献２では熱硬化性組成物の貯蔵安定性の向上のためにブロックカルボン酸を使用することを開示している。しかしながら本発明者らが、一般的なエポキシ樹脂である１，３，５−トリス（２，３−エポキシプロピル）−１，３，５−トリアジン−２，４，６−トリオンと、ブロックカルボン酸とを含む熱硬化性組成物を検討したところ、硬化時間が長いため、製造効率の点で改善の余地があることを見出した。 Patent Document 2 discloses the use of a block carboxylic acid for improving the storage stability of a thermosetting composition. However, the present inventors have found that 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione, which is a general epoxy resin, and a block carboxylic acid When the thermosetting composition containing these was examined, since the curing time was long, it discovered that there was room for improvement in terms of manufacturing efficiency.
上記を鑑みて、本発明は貯蔵安定性に優れ、かつ硬化時間の短い熱硬化性組成物を提供することを目的とする。 In view of the above, an object of the present invention is to provide a thermosetting composition having excellent storage stability and a short curing time.
上記課題を解決するため、本発明はエポキシ樹脂や硬化剤等を含む熱硬化性組成物において、前記エポキシ樹脂として２，４，６−トリ（グリシジルオキシ）−１，３，５−トリアジン［下記一般式（１）］と、前記硬化剤として下記一般式（２）で示されるブロックカルボン酸とを含有することを特徴とするものである。 In order to solve the above-mentioned problems, the present invention provides a thermosetting composition containing an epoxy resin, a curing agent and the like, and 2,4,6-tri (glycidyloxy) -1,3,5-triazine [below It contains the general formula (1)] and a block carboxylic acid represented by the following general formula (2) as the curing agent.
本発明によれば、貯蔵安定性に優れ、かつ硬化時間の短い熱硬化性組成物を提供することが可能となる。 According to the present invention, it is possible to provide a thermosetting composition having excellent storage stability and a short curing time.
＜エポキシ樹脂＞
本発明の熱硬化性組成物は、エポキシ樹脂として、２，４，６−トリ（グリシジルオキシ）−１，３，５−トリアジン（上記一般式（１））を含有することを特徴とする。かかるエポキシ樹脂と特定の硬化剤を
用いることで、熱硬化性組成物は硬化時間が短くなる。
<Epoxy resin>
The thermosetting composition of the present invention contains 2,4,6-tri (glycidyloxy) -1,3,5-triazine (the above general formula (1)) as an epoxy resin. By using such an epoxy resin and a specific curing agent, the thermosetting composition has a short curing time.
＜硬化剤＞
本発明の熱硬化性組成物は、硬化剤として上記一般式（２）で示されるブロックカルボン酸を含有することを特徴とする。上記一般式（２）で示される硬化剤は、分子内にカルボキシル基を２個含有するジカルボン酸とビニルエーテルとを付加反応させることにより得られるブロックカルボン酸である。上記一般式（２）において、Ｒ１はジカルボン酸由来の置換基であり、Ｒ２はビニルエーテル由来の置換基である。従って、ジカルボン酸とビニルエーテルとを適宜選択することにより一般式（２）におけるＲ１及びＲ２へ種々の置換基を導入することができる。かかるブロックカルボン酸と上記一般式（１）で示される特定のエポキシ樹脂を用いることで、熱硬化性組成物は貯蔵安定性が向上する。
<Curing agent>
The thermosetting composition of this invention contains the block carboxylic acid shown by the said General formula (2) as a hardening | curing agent, It is characterized by the above-mentioned. The curing agent represented by the general formula (2) is a block carboxylic acid obtained by addition reaction of a dicarboxylic acid containing two carboxyl groups in the molecule and vinyl ether. In the general formula (2), R 1 is a dicarboxylic acid-derived substituent, and R 2 is a vinyl ether-derived substituent. Therefore, various substituents can be introduced into R 1 and R 2 in the general formula (2) by appropriately selecting dicarboxylic acid and vinyl ether. By using such a block carboxylic acid and the specific epoxy resin represented by the general formula (1), the storage stability of the thermosetting composition is improved.
上記一般式（２）のＲ１が置換若しくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基を有する場合のジカルボン酸としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸等が挙げられる。上記一般式（２）のＲ１が置換若しくは無置換の炭素数３〜１０の脂環式脂肪族炭化水素基を有する場合のジカルボン酸としては、１，９−ノナンジカルボン酸、１，１−シクロプロパンジカルボン酸、１，１−シクロブタンジカルボン酸、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、３−メチルヘキサヒドロフタル酸、４−メチルヘキサヒドロフタル酸、２，３−ノルボルナンジカルボン酸、１，３−アダマンタンジカルボン酸等が挙げられる。 Examples of the dicarboxylic acid when R 1 in the general formula (2) has a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, Examples include suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like. Examples of the dicarboxylic acid when R 1 in the general formula (2) has a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms include 1,9-nonanedicarboxylic acid, 1,1- Cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydro Examples include phthalic acid, 2,3-norbornane dicarboxylic acid, 1,3-adamantane dicarboxylic acid, and the like.
上記一般式（２）のＲ２が置換若しくは無置換の炭素数１〜１０の直鎖状脂肪族炭化水素基を有する場合のビニルエーテルとしては、エチルビニルエーテル、イソプロピルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、２−エチルヘキシルビニルエーテル等が挙げられる。上記一般式（２）のＲ２が置換若しくは無置換の炭素数３〜１０の脂環式脂肪族炭化水素基を有する場合のビニルエーテルとしては、シクロヘキシルビニルエーテル、ノルボルニルビニルエーテルなどが挙げられる。 Examples of the vinyl ether when R 2 in the general formula (2) has a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n- Examples include butyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. Examples of the vinyl ether when R 2 in the general formula (2) has a substituted or unsubstituted alicyclic aliphatic hydrocarbon group having 3 to 10 carbon atoms include cyclohexyl vinyl ether and norbornyl vinyl ether.
一般式（２）で表される硬化剤は、前記ジカルボン酸の少なくとも１種と前記ビニルエーテルの少なくとも１種とを、溶媒中、６０〜１００℃の温度で反応させることにより得られる。 The curing agent represented by the general formula (2) is obtained by reacting at least one dicarboxylic acid and at least one vinyl ether in a solvent at a temperature of 60 to 100 ° C.
本発明の熱硬化性組成物には、必要に応じて、本発明の効果を損なわない範囲で各種添加剤を使用することができる。例えば添加剤として、硬化促進剤、無機充填剤、酸化防止剤、可塑剤等が挙げられる。 In the thermosetting composition of the present invention, various additives can be used as necessary as long as the effects of the present invention are not impaired. For example, examples of the additive include a curing accelerator, an inorganic filler, an antioxidant, and a plasticizer.
以下、本発明の内容を、実施例を挙げてより具体的に説明するが、本発明は下記の実施例に限定されるものではない。 Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
（製造例１）
脱イオン水中にＨＮ−５５００（日立化成社製）を添加し混合液を作製する。混合液の温度を６０℃に調整し４時間攪拌した。混合液をろ過し、白色固体を取り出した。減圧乾燥により白色固体中の水分を除き、メチルヘキサヒドロフタル酸を得た。
(Production Example 1)
HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) is added to deionized water to prepare a mixed solution. The temperature of the mixture was adjusted to 60 ° C. and stirred for 4 hours. The mixture was filtered to take out a white solid. Water in the white solid was removed by drying under reduced pressure to obtain methyl hexahydrophthalic acid.
（製造例２）
ＭＩＢＫ溶媒に、製造例１のメチルヘキサヒドロフタル酸を１当量、ｎ−プロピルビニルエーテル（日本カーバイド工業社製）を３当量加え、６５℃で4時間反応した。分液抽出及び減圧留去により、溶媒及び未反応の化合物を除き硬化剤Aを作製した。このときの収率は約９０％であった。
(Production Example 2)
To the MIBK solvent, 1 equivalent of methyl hexahydrophthalic acid of Production Example 1 and 3 equivalents of n-propyl vinyl ether (manufactured by Nippon Carbide Industries, Ltd.) were added and reacted at 65 ° C. for 4 hours. Curing agent A was prepared by removing the solvent and unreacted compound by liquid separation extraction and distillation under reduced pressure. The yield at this time was about 90%.
（製造例３）
n-プロピルビニルエーテルの代わりにシクロヘキシルビニルエーテル（日本カーバイド工業社製）を用いた以外は、製造例２と同様にして硬化剤Ｂを作製した。このときの収率は約９０％であった。
(Production Example 3)
A curing agent B was produced in the same manner as in Production Example 2 except that cyclohexyl vinyl ether (manufactured by Nippon Carbide Industries, Ltd.) was used instead of n-propyl vinyl ether. The yield at this time was about 90%.
（製造例４）
メチルヘキサヒドロフタル酸の代わりにアジピン酸（和光純薬工業社製）を用いた以外は、製造例２と同様にして硬化剤Ｃを作製した。このときの収率は約９０％であった。
(Production Example 4)
A curing agent C was prepared in the same manner as in Production Example 2 except that adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of methylhexahydrophthalic acid. The yield at this time was about 90%.
(実施例１〜３、比較例１〜４)
表１に示した組成の通りにエポキシ樹脂と硬化剤とを配合し、さらに均一に混合し、熱硬化性組成物を得た。
(Examples 1-3, Comparative Examples 1-4)
As shown in Table 1, an epoxy resin and a curing agent were blended and mixed uniformly to obtain a thermosetting composition.
前記実施例１〜３及び比較例１〜４で得られた熱硬化性組成物の物性は、以下の手法で評価した。 The physical properties of the thermosetting compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated by the following methods.
（２）硬化時間の測定
実施例１〜３、及び比較例１〜４の熱硬化性組成物について、１８０℃におけるゲル化時間をＪＩＳＣ２１６１により測定した。ここではゲル化時間の３倍の時間を硬化時間とした。
(2) Measurement of curing time About the thermosetting composition of Examples 1-3 and Comparative Examples 1-4, the gelation time in 180 degreeC was measured by JISC2161. Here, the time 3 times the gelation time was taken as the curing time.
表１中の略号は以下の通りである。
ＴＧＣ：トリグリシジルシアヌレート（２，４，６−トリ（グリシジルオキシ）−１，３，５−トリアジン、日本カーバイド工業社製）
ＴＥＰＩＣ−Ｓ：トリグリシジルイソシアヌレート（１，３，５−トリス（２，３−エポキシプロピル）−１，３，５−トリアジン−２，４，６−トリオン、日産化学社製）
硬化剤Ａ：製造例２の化合物
硬化剤Ｂ：製造例３の化合物
硬化剤Ｃ：製造例４の化合物
硬化剤Ｄ：リカシッドＭＨ−７００（メチルヘキサヒドロ無水フタル酸、新日本理化社製）
硬化剤Ｅ：リカシッドＣＨＤＡ（１，４−シクロヘキサンジカルボン酸、新日本理化社製）
Abbreviations in Table 1 are as follows.
TGC: Triglycidyl cyanurate (2,4,6-tri (glycidyloxy) -1,3,5-triazine, manufactured by Nippon Carbide Industries, Ltd.)
TEPIC-S: Triglycidyl isocyanurate (1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6-trione, manufactured by Nissan Chemical Co., Ltd.)
Curing agent A: Compound curing agent B of Production Example 2: Compound curing agent C of Production Example 3: Compound curing agent D of Production Example 4 D: Ricacid MH-700 (Methylhexahydrophthalic anhydride, manufactured by Shin Nippon Rika)
Curing agent E: Ricacid CHDA (1,4-cyclohexanedicarboxylic acid, manufactured by Shin Nippon Rika Co., Ltd.)
表１の結果より、実施例１〜３における貯蔵安定性は、いずれも比較例１〜４における貯蔵安定性よりも優れていることが分かった。また、硬化時間についても、実施例１〜３の硬化時間は比較例１〜４の硬化時間より短いことが分かった。従って、本発明の熱硬化性組成物は、貯蔵安定性に優れ、短時間で効率よく樹脂硬化物を得られることが確認された。 From the results of Table 1, it was found that the storage stability in Examples 1 to 3 was superior to the storage stability in Comparative Examples 1 to 4. Moreover, also about hardening time, it turned out that the hardening time of Examples 1-3 is shorter than the hardening time of Comparative Examples 1-4. Therefore, it was confirmed that the thermosetting composition of this invention is excellent in storage stability and can obtain a resin cured material efficiently in a short time.
本発明の熱硬化性組成物は、貯蔵安定性に優れるため長時間保存することができ、短時間で効率よく硬化することから、光半導体素子を収納するためのパッケージ材料等に用いることが可能であり、パッケージ等の生産性に優れるものである。 Since the thermosetting composition of the present invention is excellent in storage stability, it can be stored for a long time and can be efficiently cured in a short time, so that it can be used as a packaging material for housing an optical semiconductor element. It is excellent in productivity of packages and the like.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156178A (en) * | 1991-05-29 | 1993-06-22 | Rohm & Haas Co | Thermosetting powder coating composition |
| JP2001350010A (en) * | 2000-06-06 | 2001-12-21 | Nof Corp | Coating liquid for protective film of color filter and the color filter |
| JP2004339333A (en) * | 2003-05-14 | 2004-12-02 | Nof Corp | Thermosetting ink, method for producing color filter, color filter and display panel |
| JP2005099404A (en) * | 2003-09-25 | 2005-04-14 | Nof Corp | Thermosetting resin composition for planarization film of color filter and its application |
| JP2006070266A (en) * | 2004-08-06 | 2006-03-16 | Nippon Shokubai Co Ltd | Method for producing resin composition and resin composition |
| JP2009041028A (en) * | 2001-09-14 | 2009-02-26 | Sumitomo Chemical Co Ltd | Resin composition for optical-semiconductor encapsulation |
-
2013
- 2013-06-25 JP JP2013132278A patent/JP6125349B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05156178A (en) * | 1991-05-29 | 1993-06-22 | Rohm & Haas Co | Thermosetting powder coating composition |
| JP2001350010A (en) * | 2000-06-06 | 2001-12-21 | Nof Corp | Coating liquid for protective film of color filter and the color filter |
| JP2009041028A (en) * | 2001-09-14 | 2009-02-26 | Sumitomo Chemical Co Ltd | Resin composition for optical-semiconductor encapsulation |
| JP2004339333A (en) * | 2003-05-14 | 2004-12-02 | Nof Corp | Thermosetting ink, method for producing color filter, color filter and display panel |
| JP2005099404A (en) * | 2003-09-25 | 2005-04-14 | Nof Corp | Thermosetting resin composition for planarization film of color filter and its application |
| JP2006070266A (en) * | 2004-08-06 | 2006-03-16 | Nippon Shokubai Co Ltd | Method for producing resin composition and resin composition |
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