JPS6049024A - Curing of epoxy resin - Google Patents

Curing of epoxy resin

Info

Publication number
JPS6049024A
JPS6049024A JP15848683A JP15848683A JPS6049024A JP S6049024 A JPS6049024 A JP S6049024A JP 15848683 A JP15848683 A JP 15848683A JP 15848683 A JP15848683 A JP 15848683A JP S6049024 A JPS6049024 A JP S6049024A
Authority
JP
Japan
Prior art keywords
diamino
component
triazine
ethyl
alkylimidazolyl
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.)
Granted
Application number
JP15848683A
Other languages
Japanese (ja)
Other versions
JPS6242929B2 (en
Inventor
Kazuo Kamagata
鎌形 一夫
Takashi Mizui
水井 隆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shikoku Chemicals Corp
Original Assignee
Shikoku Chemicals Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shikoku Chemicals Corp filed Critical Shikoku Chemicals Corp
Priority to JP15848683A priority Critical patent/JPS6049024A/en
Publication of JPS6049024A publication Critical patent/JPS6049024A/en
Publication of JPS6242929B2 publication Critical patent/JPS6242929B2/ja
Granted legal-status Critical Current

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  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Insulating Materials (AREA)

Abstract

PURPOSE:To obtain a cured epoxy resin having excellent heat resistance, by mixing a polyepoxy resin with 2,4-diamino-6-[2'-alkylimidazolyl(1)']ethyl-S-triazine, etc. as a hardener and a specific polymerizable monomer, etc., and heating the mixture. CONSTITUTION:A polyepoxy compound having one or more epoxy groups in a molecule is mixed with (B) a hardener comprising 2,4-diamino-6-[2'-alkylimidazolyl(1)']ethyl-S-triazine or an isocyanuric acid adduct of 2,4-diamino-6-[2'-alkylimidazolyl(1)']ethyl-S-triazine, (C) a polymerizable monomer comprising 2,4-diamino-6-vinyl-S-triazine and (D) a polymerization initiator, and the mixture is heated to obtain the objective opoxy resin. Preferably, the amount of the component B is 3-10pts.wt. per 100pts.wt. of the component A, that of the component C is 5-100mol% of the component A, and that of the component D is 0.5-1.0% of the component C.

Description

【発明の詳細な説明】 本範明は分子中に平均1個より多くのエポキシ基を有す
るエポキシ化合物を硬化させる方法に関するもので、そ
の目的とする処はポリエポキシ化合物阜址体と硬化剤が
混合さnた系の室温におけるボッ■・ライフが長く、そ
の系の硬化に際して所望の温度に加熱すると速かpc硬
化する一液性エボキシ樹脂として使用することができ且
つ硬化した樹脂に優れた耐熱性を付与させることにある
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for curing an epoxy compound having an average of more than one epoxy group in the molecule, and its purpose is to cure a polyepoxy compound and a curing agent mixed together. It has a long bottle life at room temperature, can be used as a one-component epoxy resin that quickly cures when heated to the desired temperature, and the cured resin has excellent heat resistance. The purpose is to grant the following.

本発明方法は電子部品封止材料、絶縁材料及び接〉7剤
等に適応してf#著な効呆を発弾することができる。
The method of the present invention can be applied to electronic component sealing materials, insulating materials, adhesives, etc., and can exhibit significant f# effects.

ポリエポキシ化合物の硬化に当り、−1ミダゾ一ル系化
合物を配合すると作業性の良い一液性組成物となり、相
当の耐熱性を有する樹脂を与えることが知らnているけ
れども、′−子部品の製造などにあってはその小型化、
高密度化に伴なり史に作業性、耐熱性等を向上させるこ
とが要求されている。
When curing polyepoxy compounds, it is known that blending -1 midazole compounds results in a one-component composition with good workability and a resin with considerable heat resistance. In the manufacturing of
As density increases, improvements in workability, heat resistance, etc. are required.

不発町名等は、この事1′gに鑑み耐熱性の高い一液性
エボキシ樹脂を1指して鋭意検討を重ねた結果、分子中
に平均1ケより多くのエポキシ基を有するポリエポキシ
化合物に、硬化剤として次式で示される2、4−ジアミ
ノ−6−(2’−アルキルイミダゾリル(1)’ ]エ
チル−8−ト’Jアシン式 (但し、式1すはアルギル基、R′は水素原子又はアル
ギル基を示す) 又tま次式で示される2、4−ジアミノ−6−(2’−
アルキルイミダゾリル(1)’)エチル−8−)!Jア
ジンイソシアヌル酸付加物 (但し式中)t 、 R’は前記と同じ)と、2,4−
ジアミノ−6−ピニルー8−)リアジン及び−足合性モ
ノマーのili合翻合剤始剤合して加iihすることに
より所期の目的を達成したもの−Cある。
In light of this fact, the name of the unexploded town, etc., was determined after intensive study on a one-component epoxy resin with high heat resistance. As a curing agent, 2,4-diamino-6-(2'-alkylimidazolyl(1)')ethyl-8-to'Jacine formula shown by the following formula (wherein formula 1 is an argyl group and R' is hydrogen 2,4-diamino-6-(2'-
Alkylimidazolyl(1)')ethyl-8-)! J azine isocyanuric acid adduct (wherein t and R' are the same as above) and 2,4-
The desired objective was achieved by adding a combination of diamino-6-pinyl-8-) riazine and a conjugating monomer with a conjugating agent initiator.

氷見りi方法によって生じるエポキシ樹脂硬化物に優れ
た耐熱性が付与さnる理由については、ポリエポキシ化
合物とイミダゾール化合物を加熱するとアニオン重合し
て三次元網目構造をつくり、またビニルトリアジンは重
合開始剤の存在下に加熱するとラジカル重合して耐熱性
の高い線状高分子となることから、エポキシ樹脂の三次
元網目の中に、2.4−ジアミノ−6−ピニルー8−)
リアジンの固い鎖が交差して、工P N (Intθr
Penetrated Network )構造を形成
するためと思われる。
The reason why the epoxy resin cured product produced by the Himi method has excellent heat resistance is that when the polyepoxy compound and imidazole compound are heated, they undergo anionic polymerization to create a three-dimensional network structure, and vinyl triazine initiates polymerization. When heated in the presence of the epoxy resin, it radically polymerizes to form a linear polymer with high heat resistance.
The rigid chains of riazine intersect and form
This is thought to be due to the formation of a penetrated network structure.

本発明方法において特定のイミダゾール化合物を用いる
ことは、−液性組成物のり何時間と流動性などの作業性
及び樹脂に対する耐熱性を両立させるために不可欠であ
る〇 本発明において使用される硬化剤2,4−ジアミノ−6
−(2’−アルキルイミダゾリル(1)’)エナルー1
3−)リアジンは、特公昭47−36391号公報に記
載の方法によって合成することができ、その代表的なも
のは2・4−ジアミノ−6−(2′−メチルイミダゾリ
ル(1)’)エチル−S−トリアジン、2.4−ジアミ
ノ−6−(2’−エチル4′−メチルイミダゾリル(X
)’ )エチル−8−)リアジン、2・4−ジアミノ−
6−(2’−クンデシルイミダゾリル(1)’)エテル
−8−)リアジン等であり、また鹸化剤2,4−ジアミ
ノ−6−(2’−アルギルイミダゾリル(1)’)エチ
ル−8−)リアジンイノシアヌル酸付加v!Jは、特公
昭56−19514号公報に記載の方法によって製造す
ることができ、その代表的なものは2゜4−ジアミノ−
6−(2’−メチルイミダゾリル(1)’ ) 工fル
ーs −トyアジンイソシアヌル酸付加物、2,4−ジ
アミノ−6−(2’−エチル−4′−メチルイミダゾリ
ル(1)’)エチル−S−トリアジンインシアヌル績付
加物等である。これら級化剤の使用量は、ポリエポキシ
化合物100皿■部に対して3〜10蔗址部の割合が適
当である。
The use of a specific imidazole compound in the method of the present invention is essential in order to achieve both workability such as shelf life and fluidity of the liquid composition, and heat resistance for the resin.〇Curing agent used in the present invention 2,4-diamino-6
-(2'-alkylimidazolyl(1)')enalu 1
3-) Riazine can be synthesized by the method described in Japanese Patent Publication No. 47-36391, and a representative example thereof is 2,4-diamino-6-(2'-methylimidazolyl(1)')ethyl -S-triazine, 2,4-diamino-6-(2'-ethyl 4'-methylimidazolyl (X
)' ) Ethyl-8-)riazine, 2,4-diamino-
6-(2'-cundecylimidazolyl (1)') ether-8-) liazine, etc., and the saponifying agent 2,4-diamino-6-(2'-argylimidazolyl (1)') ethyl-8 -) Addition of riazine inocyanuric acid v! J can be produced by the method described in Japanese Patent Publication No. 56-19514, and a typical example thereof is 2゜4-diamino-
6-(2'-Methylimidazolyl(1)') Engineering f-ruz-yazine isocyanuric acid adduct, 2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl(1)') and ethyl-S-triazine cyanuric adducts. The appropriate amount of these grading agents to be used is 3 to 10 parts per 100 parts of the polyepoxy compound.

また雉合性七ツマ−の2.4−ジアミノ−6−ビニル−
B−)リアジンに:tポリエポキシ化合物に対して5〜
100そル%の範囲で配合することができる。
Also, 2,4-diamino-6-vinyl-
B-) To riazine: 5 to 5 to t polyepoxy compound
It can be blended in a range of 100%.

2.4−ジアミノ−6−ビニル−S−トリアジンの重合
開始剤としては一般的に知ら扛ている有機過酸化物、無
機過酸化物、アゾイソブチルニトリル等であり、これら
のうち経時変化が少なく且つ取扱いが各易なジクミルパ
ーオキサイドは特に好適である。
As polymerization initiators for 2.4-diamino-6-vinyl-S-triazine, commonly known organic peroxides, inorganic peroxides, azoisobutylnitrile, etc. are used, and among these, those that change less over time Dicumyl peroxide is particularly suitable because it is easy to handle.

重合開始剤の使用量は、2.4−ジアミノ−6−ビニル
−S−トリアジンに対して0.5〜1.096が適当で
ある。
The appropriate amount of the polymerization initiator to be used is 0.5 to 1.096 to 2,4-diamino-6-vinyl-S-triazine.

本発明の実施に当っては、前記主成分の他に炭酸カルシ
ウム、タルク、アルミナ、シリカ停の無機質充填剤及び
顔料、染料等の着色剤等を添加しても差し支えない。
In carrying out the present invention, in addition to the above-mentioned main components, inorganic fillers such as calcium carbonate, talc, alumina, and silica, and coloring agents such as pigments and dyes may be added.

本発明方法は、各成分を予め均一に混合した一液型組成
物とするほかに、硬化剤ないし重合開始剤を反応の直前
に配合することも可能であり、均一に配合された組成物
は約90〜150℃の温度に数時間加熱することによっ
て硬化反応を完了することができる。
In the method of the present invention, in addition to forming a one-component composition in which each component is uniformly mixed in advance, it is also possible to mix a curing agent or a polymerization initiator immediately before the reaction. The curing reaction can be completed by heating to a temperature of about 90-150°C for several hours.

以下実施例及び参考例をもって本発明を具体的にi、り
λ明する。
The present invention will be explained in detail below using Examples and Reference Examples.

災’AMi 11y+J 1゜ ビスフェノールへのジグリンジルエーテル〔商品名[エ
ボミツクn−14DJ(三片石油化学エボA−ン)1[
]]Og;、2.4−ジ゛γミノ−6(2’−メチルイ
ミダゾリル(1)’)エチル−s−トリアジン5g、2
.1−ジアミノ−6−ピニルーS−トす7973.15
g5 ジクミルパーオキサイド〔商品名「パークミルD
−4DJ(日本油)M ) 、10.1g(ビニルトリ
アジンに対するモル比0.5%)及び枯i iJ4 壁
剤〔商品名[エロジル番’500J(日本エアロジル)
1gを三本ロールミルで均一に分数混合してエポキシ樹
脂組成物を形成した。
Disaster'AMi 11y+J 1゜Digrindyl ether to bisphenol [Product name [Ebomitsuku n-14DJ (Mikata Petrochemical EvoA-n)] 1[
]]Og;, 2,4-di-γmino-6(2'-methylimidazolyl(1)')ethyl-s-triazine 5g, 2
.. 1-Diamino-6-pinyl S-tosu 7973.15
g5 Dicumyl peroxide [Product name: Percmil D
-4DJ (Japan Oil) M), 10.1g (0.5% molar ratio to vinyltriazine) and dried iJ4 wall agent [trade name [Erosil No.'500J (Japan Aerosil)]
An epoxy resin composition was prepared by uniformly mixing 1 g in fractions in a three-roll mill.

氷晶の25′Cにおける粘度は3,200cps。The viscosity of ice crystals at 25'C is 3,200 cps.

40′Gの温度に1週間放−した粘度上昇率は22’3
.、.150°Cの温度で加熱した場合のゲルタイムは
2分10秒であり、これを90℃の温度で4時間、更に
150’O(iり瀉屁で4時間した硬化物は、ガラス転
移点166’C,熱・変形温[(、T工5K−7207
)1/)1’C,25’Cにお0る曲は強度(J I 
5K−7205) 7.7Kg/LIIIl、150’
Cにおける曲げ強度1.8 Kg /mtを示しに0参
考例 前記実施例において、2.4−ジアミノ−6−ピニルー
8−)リアジン及びジクミルパーオキサイドを添加せず
に同様の処理を行なった結果、未硬化のエポキシ樹脂組
成物は枯)X3,10ocpI3(25’C)粘度上昇
率179ム、ゲルタイム2分35秒であり、その硬化物
は、ガラス転移点f 24 ’c熱j形温度1ろ1′C
1曲は強度乙4 ”g/haz (25’C)、0.7
 Kg/u& (150’C) テあッ7IC0実施例
2 実施例1において、硬化剤2.4−ジアミノ−6=(2
’−メチルイミダゾリル(1)’)エチル−s−トリア
ジンを2.4−ジアミノ−6−(2’−メチルイミダゾ
リル(1)Mエテル−f3− ) リアジンインシアヌ
ル酸付加物に変えた以外(使用閂は同じ)は全く同様の
配合で処理し、また同一条件で諸性質を調べたところ、
未硬化のエポキシ樹脂組成物は粘度3.500 cps
 (25℃)、粘度上+4率5%、ゲルタイム1分20
秒であり、その硬化物をまガラス転移点170“C1熱
変形温度166’O% 曲げ弓、′Li度9.71(g
/ll、11(25’C)、2.1Kg/m(150’
C)’を示した。
The rate of increase in viscosity after being left at a temperature of 40'G for one week was 22'3.
.. ,. The gel time when heated at a temperature of 150°C is 2 minutes 10 seconds, and the cured product heated at a temperature of 90°C for 4 hours and further 4 hours at 150°C has a glass transition point of 166 'C, heat/deformation temperature [(, T engineering 5K-7207
)1/) Songs that fall at 1'C and 25'C have an intensity (J I
5K-7205) 7.7Kg/LIIIl, 150'
Reference Example The same treatment as in the above example was carried out without adding 2,4-diamino-6-pinyl-8-) riazine and dicumyl peroxide. As a result, the uncured epoxy resin composition had a viscosity increase rate of 179 μm and a gel time of 2 minutes and 35 seconds at 25'C, and the cured product had a glass transition point of f24'c. 1ro 1'C
One song has a strength of 4"g/haz (25'C), 0.7
Kg/u&(150'C) Teat7IC0 Example 2 In Example 1, the curing agent 2.4-diamino-6=(2
Except that '-methylimidazolyl(1)') ethyl-s-triazine was changed to 2,4-diamino-6-(2'-methylimidazolyl(1)M ether-f3-) riazine in cyanuric acid adduct ( The same bolts were used) were treated with exactly the same formulation, and the properties were examined under the same conditions.
The uncured epoxy resin composition has a viscosity of 3.500 cps.
(25℃), viscosity +4 rate 5%, gel time 1 minute 20
The cured product has a glass transition point of 170, a thermal deformation temperature of 166'O%, a bending bow, and a Li degree of 9.71 (g
/ll, 11 (25'C), 2.1Kg/m (150'
C)' was shown.

特許出願人 四国化成工桑株式会社patent applicant Shikoku Kasei Koso Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 分子中に平均1ケより多くのエポキシ基を有するポリエ
ポキシ化合物に、硬化剤としての2.4−ジアミノ−6
−[2’ −アルキルイミダゾリル(1)’)エチル−
s−トリアジン又は2・4−ジアミノ−6−(2’−ア
ルノルイミダゾリル(1)’)エテル−S−トVアジン
イソンアヌル酸付加物と2.4−ジアミノ−6−ピニル
ー8−)リアジン及び該1j゛合性モノマーの重合開始
剤を混合して加熱することを特徴とするエポキシ樹脂硬
化方法。
2,4-diamino-6 as a curing agent for polyepoxy compounds having an average of more than one epoxy group in the molecule.
-[2'-alkylimidazolyl(1)')ethyl-
s-triazine or 2,4-diamino-6-(2'-alnolimidazolyl(1)') ether-S-toV azineisoanuric acid adduct and 2,4-diamino-6-pinyl-8-) liazine and an epoxy resin curing method, which comprises mixing and heating a polymerization initiator for the 1j polymerizable monomer.
JP15848683A 1983-08-29 1983-08-29 Curing of epoxy resin Granted JPS6049024A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15848683A JPS6049024A (en) 1983-08-29 1983-08-29 Curing of epoxy resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15848683A JPS6049024A (en) 1983-08-29 1983-08-29 Curing of epoxy resin

Publications (2)

Publication Number Publication Date
JPS6049024A true JPS6049024A (en) 1985-03-18
JPS6242929B2 JPS6242929B2 (en) 1987-09-10

Family

ID=15672789

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15848683A Granted JPS6049024A (en) 1983-08-29 1983-08-29 Curing of epoxy resin

Country Status (1)

Country Link
JP (1) JPS6049024A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6243413A (en) * 1985-08-20 1987-02-25 Hitachi Chem Co Ltd Thermosetting resin composition
JPS62148518A (en) * 1985-12-23 1987-07-02 Mitsui Toatsu Chem Inc One-pack type epoxy resin composition
WO2001046288A1 (en) * 1999-12-22 2001-06-28 Taiyo Ink Manufacturing Co., Ltd. Resin composition curable with actinic energy ray
JP2001240609A (en) * 2000-02-29 2001-09-04 Taiyo Ink Mfg Ltd Active energy ray curable resin composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03130330U (en) * 1990-04-16 1991-12-27
JPH079286A (en) * 1993-06-30 1995-01-13 Mitsubishi Motors Corp Thrust metal installing device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6243413A (en) * 1985-08-20 1987-02-25 Hitachi Chem Co Ltd Thermosetting resin composition
JPH0430965B2 (en) * 1985-08-20 1992-05-25
JPS62148518A (en) * 1985-12-23 1987-07-02 Mitsui Toatsu Chem Inc One-pack type epoxy resin composition
WO2001046288A1 (en) * 1999-12-22 2001-06-28 Taiyo Ink Manufacturing Co., Ltd. Resin composition curable with actinic energy ray
JP2001240609A (en) * 2000-02-29 2001-09-04 Taiyo Ink Mfg Ltd Active energy ray curable resin composition
JP4713704B2 (en) * 2000-02-29 2011-06-29 太陽ホールディングス株式会社 Active energy ray-curable resin composition

Also Published As

Publication number Publication date
JPS6242929B2 (en) 1987-09-10

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