JPH052690B2 - - Google Patents
Info
- Publication number
- JPH052690B2 JPH052690B2 JP22005384A JP22005384A JPH052690B2 JP H052690 B2 JPH052690 B2 JP H052690B2 JP 22005384 A JP22005384 A JP 22005384A JP 22005384 A JP22005384 A JP 22005384A JP H052690 B2 JPH052690 B2 JP H052690B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- methylimidazole
- epoxy resin
- curing agent
- terpene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000003822 epoxy resin Substances 0.000 claims description 29
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 235000007586 terpenes Nutrition 0.000 claims description 21
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 20
- 150000003505 terpenes Chemical class 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008096 xylene Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- -1 boron trifluoride amine Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000000899 Gutta-Percha Substances 0.000 description 1
- 240000000342 Palaquium gutta Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000588 gutta-percha Polymers 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Description
産業上の利用分野
本発明はエポキシ樹脂用硬化剤、特に２−メチ
ルイミダゾールを使用したエポキシ樹脂用硬化剤
の製造方法に関する。
従来の構成とその問題点
エポキシ樹脂は広汎な材料の接着、塗装、電子
部品の封止、含浸用成形材料等各種産業分野で広
く利用されている。
従来かかるエポキシ樹脂の固体硬化剤として
は、酸無水物、アミン類、ポリアミド樹脂、ジシ
アンジアミド、三弗化硼素アミンコンプレツクス
あるいはイミダゾールの如き潜在性硬化剤が用い
られている。
これらの硬化剤はエポキシ樹脂と混合して一体
粉体型組成物として用いる場合には、何れも貯蔵
安定性と硬化性とが両立しないという問題点を有
していた。即ち低温で迅速硬化性を有する硬化剤
は貯蔵安定性が悪く、逆に貯蔵安定性の良い潜在
性硬化剤は、硬化に高温長時間を要し、低温迅速
硬化性に欠ける欠点を有していた。
発明の目的
本発明は上述した如き固体の潜在硬化剤の欠点
を克服し、エポキシ樹脂と混合して一体粉体型組
成物とした時、貯蔵安定性が優れ、しかも比較的
低温で加熱したとき迅速硬化の可能なエポキシ樹
脂用硬化剤の製造方法を提供することにある。
発明の構成
本発明は、２−メチルイミダゾールとテルペン
樹脂またはキシレン樹脂とを、２−メチルイミダ
ゾールを融解せず、かつテルペン樹脂またはキシ
レン樹脂を融解する温度で加熱混合し、冷却固化
させた後粉砕することからなるエポキシ樹脂用硬
化剤の製造方法にある。
２−メチルイミダゾールは従来より迅速硬化剤
として使用されており、融点145℃を有する常温
で固体の材料である。しかしながらこの材料をエ
ポキシ樹脂と混合して一体粉体型組成物としたと
き貯蔵安定性が悪い。
またテルペン樹脂またはキシレン樹脂は硬化剤
としての性質は有していないが、エポキシ樹脂と
の相溶性が良好である。このためエポキシ樹脂に
これらの樹脂が混入してもエポキシ樹脂との相分
離を生ずることなく、エポキシ樹脂成形物に悪影
響を与えることがない。
本発明によれば２−メチルイミダゾールを、こ
れより融点の低い、そしてエポキシ樹脂との相溶
性の良好なテルペン樹脂またはキシレン樹脂と共
に、２−メチルイミダゾールは融解せず、テルペ
ン樹脂またはキシレン樹脂は融解する温度で加熱
混合することにより、２−メチルイミダゾールの
粉末ないし粒子をテルペン樹脂またはキシレン樹
脂で被覆させるのである。かくして形成された硬
化剤２−メチルイミダゾールはテルペン樹脂また
はキシレン樹脂の被覆を有しているため、エポキ
シ樹脂粉末と混合しても室温では２−メチルイミ
ダゾールがエポキシ樹脂と接触することがなく、
貯蔵安定性に優れた一体粉体型組成物が得られ
る。しかもこの組成物は、テルペン樹脂またはキ
シレン樹脂が融解する温度以上に加熱したとき、
始めて２−メチルイミダゾールがエポキシ樹脂と
接触して急速にエポキシ樹脂を硬化させることが
できる。また融解したテルペン樹脂またはキシレ
ン樹脂は前述した如くエポキシ樹脂との相溶性が
良好であるので硬化された組成物に悪影響を与え
ることもない。
本発明で使用するテルペン樹脂またはキシレン
樹脂は２−メチルイミダゾールより低い融点を有
し、常温で固体のものであれば任意のものが使用
でき、テルペン樹脂としては天然および合成の何
れでもよい、例えばグツタペルカ、ポリイソプレ
ンがあり、例えば日本ゼオン社製商標名クイント
ン−1500（合成テルペン樹脂の商品名）やその他
エポキシ樹脂と相溶性の良い鎖状および環状テル
ペン樹脂であれば使用できる。キシレン樹脂とし
ては例えば三菱ガス化学社製ニカノール（商品
名）がある。
本発明の硬化剤を製造するに当つては、２−メ
チルイミダゾール１重量部に対してテルペン樹脂
またはキシレン樹脂１重量部〜５重量部の割合で
使用するとよい。テルペン樹脂またはキシレン樹
脂の割合が上記値より少なくなると得られた硬化
剤をエポキシ樹脂と混合したときその貯蔵安定性
が悪くなり好ましくなく、また上記値より大なる
割合になるとテルペン樹脂またはキシレン樹脂が
エポキシ樹脂の硬化速度を遅くし、迅速硬化性を
失うので好ましくない。
実施例の説明
以下に実施例を挙げて本発明を説明する。
実施例 １
２−メチルイミダゾール（四国化成工業社製、
商品名2MZ、融点145℃）50重量部を、合成テル
ペン樹脂（日本ゼオン社製、商品名クイントン−
1500、融点100℃）100重量部と混合し、120℃に
加熱し、均一撹拌した後、冷却固化させ、乳鉢に
て粉砕し、粉末硬化剤を得た。
次にエポキシ当量450〜500の室温で固体のビス
フエノールＡ型エポキシ樹脂（油化シエル社製、
商品名エピコート1001）100重量部に、上述した
如くして作つた硬化剤15重量部を加え、ボールミ
ルで混合した。
このエポキシ樹脂組成物を用いて、２枚のアル
ミニウム板を2.5cm2の面積で貼り合せ、120℃で20
分硬化後、オートグラフでせん断接着強度を測定
したところ170Kg／cm2であつた。
また上記エポキシ樹脂組成物は、室温で１カ月
保存した後でも接着試験の結果接着力の低下は見
られなかつた。
また120℃におけるゲル化時間は、作成時に１
分30秒であつたものが室温１カ月保存後は、１分
40秒であり、ほとんど変化は見られなかつた。
実施例 ２
２−メチルイミダゾール（商品名2MZ）50重
量部を、キシレン樹脂（三菱ガス化学社製、商品
名ニカノール、融点70〜100℃）100重量部と混合
し、120℃に加熱し、均一撹拌した後、冷却固化
させ、乳鉢で粉砕して粉末硬化剤を得た。
次にエポキシ当量450〜500の室温で固体のビス
フエノールＡ型エポキシ樹脂（商品名エピコート
1001）100重量部に、上述した如く作つた硬化剤
15重量部を加え、ボールミルで混合した。
このエポキシ樹脂組成物を用いて実施例１に示
した如くアルミニウム板を貼り合せ、120℃で20
分硬化後のせん断接着力を測定したところ150
Kg／cm2であつた。またこの組成物は５℃で３カ月
保存した後でも接着試験の結果、接着力の低下は
見られなかつた。
また120℃におけるゲル時間は、作成時に１分
25秒であつたものが５℃３カ月保存後も１分30秒
でありほとんど変化は見られなかつた。
下表１に上記実施例１および２の結果を集約し
て示す。
なお表１には室温で１カ月、５℃で３カ月貯蔵
した後のデータも示す。また表１に比較例とし
て、テルペン樹脂またはキシレン樹脂を使用せ
ず、２−メチルイミダゾールをそのまま使用した
場合のデータも示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a curing agent for epoxy resins, particularly to a method for producing a curing agent for epoxy resins using 2-methylimidazole. Conventional configurations and their problems Epoxy resins are widely used in various industrial fields such as adhesion of a wide range of materials, painting, sealing of electronic parts, and impregnating molding materials. Hitherto, latent curing agents such as acid anhydrides, amines, polyamide resins, dicyandiamide, boron trifluoride amine complexes, and imidazole have been used as solid curing agents for such epoxy resins. When these curing agents are mixed with an epoxy resin and used as an integrated powder composition, they all have the problem that storage stability and curability are not compatible. In other words, curing agents that cure rapidly at low temperatures have poor storage stability, while latent curing agents that have good storage stability have the disadvantage of requiring a long period of time to cure at high temperatures and lacking rapid curing properties at low temperatures. Ta. Purpose of the Invention The present invention overcomes the drawbacks of the solid latent curing agent as described above, and when mixed with an epoxy resin to form an integrated powder composition, has excellent storage stability and when heated at a relatively low temperature. An object of the present invention is to provide a method for producing a curing agent for epoxy resin that can be rapidly cured. Structure of the Invention The present invention involves heating and mixing 2-methylimidazole and a terpene resin or xylene resin at a temperature that does not melt the 2-methylimidazole but melts the terpene resin or xylene resin, cools and solidifies, and then pulverizes the resin. There is a method for producing a curing agent for epoxy resin, which comprises the steps of: 2-Methylimidazole has been conventionally used as a rapid curing agent, and is a solid material at room temperature with a melting point of 145°C. However, when this material is mixed with an epoxy resin to form an integral powder composition, the storage stability is poor. Further, terpene resin or xylene resin does not have properties as a curing agent, but has good compatibility with epoxy resin. Therefore, even if these resins are mixed into the epoxy resin, phase separation with the epoxy resin will not occur, and the epoxy resin molded product will not be adversely affected. According to the present invention, when 2-methylimidazole is combined with a terpene resin or xylene resin that has a lower melting point and has good compatibility with the epoxy resin, the 2-methylimidazole does not melt, and the terpene resin or xylene resin melts. The 2-methylimidazole powder or particles are coated with the terpene resin or xylene resin by heating and mixing at a temperature of 2-methylimidazole. Since the curing agent 2-methylimidazole thus formed has a coating of terpene resin or xylene resin, even when mixed with epoxy resin powder, 2-methylimidazole does not come into contact with the epoxy resin at room temperature.
An integrated powder composition with excellent storage stability is obtained. Moreover, when this composition is heated above the temperature at which the terpene resin or xylene resin melts,
For the first time, 2-methylimidazole comes into contact with the epoxy resin and can rapidly cure the epoxy resin. Furthermore, since the melted terpene resin or xylene resin has good compatibility with the epoxy resin as described above, it does not adversely affect the cured composition. The terpene resin or xylene resin used in the present invention can be any resin as long as it has a lower melting point than 2-methylimidazole and is solid at room temperature.The terpene resin can be either natural or synthetic, e.g. Examples include gutta percha and polyisoprene; for example, Quinton-1500 (trade name of a synthetic terpene resin) manufactured by Nippon Zeon Co., Ltd. and other chain and cyclic terpene resins that are compatible with epoxy resins can be used. Examples of the xylene resin include Nicanol (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd. When producing the curing agent of the present invention, it is preferable to use the terpene resin or xylene resin in a ratio of 1 to 5 parts by weight per 1 part by weight of 2-methylimidazole. If the proportion of terpene resin or xylene resin is less than the above value, the storage stability of the obtained curing agent will deteriorate when mixed with epoxy resin, which is undesirable, and if the proportion is greater than the above value, terpene resin or xylene resin may This is not preferable because it slows down the curing speed of the epoxy resin and causes it to lose its rapid curing properties. Description of Examples The present invention will be described below with reference to Examples. Example 1 2-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.,
50 parts by weight of synthetic terpene resin (product name 2MZ, melting point 145℃) was added to synthetic terpene resin (manufactured by Nippon Zeon Co., Ltd., product name
1500, melting point 100°C), heated to 120°C, stirred uniformly, cooled to solidify, and crushed in a mortar to obtain a powder hardening agent. Next, a bisphenol A type epoxy resin with an epoxy equivalent of 450 to 500 and solid at room temperature (manufactured by Yuka Ciel Co., Ltd.,
15 parts by weight of the curing agent prepared as described above was added to 100 parts by weight (trade name: Epicoat 1001) and mixed in a ball mill. Using this epoxy resin composition, two aluminum plates with an area of 2.5 cm 2 were bonded together, and
After curing for a few minutes, the shear adhesive strength was measured using an autograph and found to be 170 Kg/cm 2 . Further, the above epoxy resin composition showed no decrease in adhesive strength as a result of an adhesion test even after being stored at room temperature for one month. In addition, the gelation time at 120℃ is 1
After being stored at room temperature for 1 month, it will take 1 minute to heat up for 30 seconds.
It took 40 seconds, and almost no change was observed. Example 2 50 parts by weight of 2-methylimidazole (trade name 2MZ) was mixed with 100 parts by weight of xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol, melting point 70-100°C), heated to 120°C, and uniformly mixed. After stirring, the mixture was cooled and solidified, and crushed in a mortar to obtain a powder hardening agent. Next, a bisphenol A type epoxy resin (trade name Epicote), which is solid at room temperature and has an epoxy equivalent of 450 to 500, is
1001) 100 parts by weight of the curing agent prepared as described above.
15 parts by weight were added and mixed using a ball mill. Using this epoxy resin composition, an aluminum plate was bonded as shown in Example 1, and
The shear adhesive strength was measured after curing for 150 minutes.
It was Kg/ cm2 . Further, even after this composition was stored at 5° C. for 3 months, no decrease in adhesive strength was observed as a result of an adhesion test. Also, the gel time at 120℃ is 1 minute at the time of preparation.
The temperature was 25 seconds, but after storage at 5°C for 3 months, the temperature was 1 minute and 30 seconds, with almost no change observed. Table 1 below summarizes the results of Examples 1 and 2. Table 1 also shows data after storage at room temperature for one month and at 5°C for three months. Table 1 also shows, as a comparative example, data when 2-methylimidazole was used as it was without using terpene resin or xylene resin.
【表】
発明の効果
上述した如く、本発明による硬化剤を使用する
と、120℃で20分程度で硬化可能であり、しかも
貯蔵安定性の優れたエポキシ樹脂組成物を得るこ
とができる。これに対し、比較例では120℃で20
分という低温迅速硬化を行なわんとすると、可使
時間が室温で２〜３日と短くなり、また可使時間
が室温で１カ月程度のものは反応条件（硬化条件
が）150〜170℃で数時間と高温、長時間を必要と
し、本発明の硬化剤のすぐれていることが判る。[Table] Effects of the Invention As described above, when the curing agent according to the present invention is used, it is possible to obtain an epoxy resin composition that can be cured at 120° C. in about 20 minutes and has excellent storage stability. On the other hand, in the comparative example, 20
If you try to perform quick curing at a low temperature of 1 minute, the pot life will be shortened to 2 to 3 days at room temperature, and if the pot life is about 1 month at room temperature, the reaction conditions (curing conditions) are 150 to 170 degrees Celsius. It requires several hours of high temperature and long time, which shows that the curing agent of the present invention is superior.
Claims (1)
はキシレン樹脂とを、２−メチルイミダゾールを
融解せず、かつテルペン樹脂またはキシレン樹脂
を融解する温度で加熱混合し、冷却固化させた後
粉砕することを特徴とするエポキシ樹脂用硬化剤
の製造方法。1 2-Methylimidazole and a terpene resin or xylene resin are heated and mixed at a temperature that does not melt the 2-methylimidazole and melts the terpene resin or xylene resin, is cooled to solidify, and is then pulverized. A method for producing a curing agent for epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22005384A JPS6197321A (en) | 1984-10-18 | 1984-10-18 | Production of curing agent for epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22005384A JPS6197321A (en) | 1984-10-18 | 1984-10-18 | Production of curing agent for epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6197321A JPS6197321A (en) | 1986-05-15 |
| JPH052690B2 true JPH052690B2 (en) | 1993-01-13 |
Family
ID=16745187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22005384A Granted JPS6197321A (en) | 1984-10-18 | 1984-10-18 | Production of curing agent for epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6197321A (en) |
-
1984
- 1984-10-18 JP JP22005384A patent/JPS6197321A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6197321A (en) | 1986-05-15 |
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