JP2004018452A - New ester compound having isocyanuric acid ring, and epoxy resin composition using the compound - Google Patents
New ester compound having isocyanuric acid ring, and epoxy resin composition using the compound Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
この発明は、エポキシ樹脂の硬化剤として有用なイソシアヌル酸環を有する新規なエステル化合物および該化合物を配合したエポキシ樹脂組成物に関するものである。
【０００２】
【従来の技術】
エポキシ樹脂組成物は、種々のタイプのエポキシ樹脂と硬化剤、また必要に応じて硬化促進剤を組み合わせることにより、優れた電気特性、機械特性、熱特性を発揮させることができるため、多くの分野で使用されている。
【０００３】
エポキシ樹脂の硬化剤としては、一般的に酸無水物、フェノール化合物等の酸性化合物や、アミン、尿素、イミダゾール類等の塩基性化合物等が、硬化物の求められる特性に応じて使い分けされている。
【０００４】
酸性化合物の一つである１，３，５−トリス（２−カルボキシエチル）イソシアヌレート（以下、ＣＩＣ酸という）を硬化剤として配合したエポキシ樹脂組成物が提案されている（例えば、特開昭５９−１０７７４２号、特表平８−５０６１３４号、特開平１１−２９３１８７号、同１１−２９３１８９号、特表２００１−５０２００３号等）。
【０００５】
しかしながら、ＣＩＣ酸をエポキシ樹脂の硬化剤として使用する場合、ＣＩＣ酸が高融点（２２３〜２２６℃）であり且つエポキシ樹脂との相溶性が悪いため、均一な硬化物を得るためには２００℃以上の高い硬化温度を必要とすると云う難点がある。
即ち２００℃未満の硬化温度では、エポキシ樹脂に添加したＣＩＣ酸が固体状態のままであるので硬化反応が完結せず、得られる硬化物の諸特性が悪いのは無論であるが、未反応のＣＩＣ酸が残るので硬化物が不透明なものとなり、その外観も悪い。
【０００６】
一方、１５０℃程度の比較的低い温度で硬化させるためには、ＣＩＣ酸をエポキシ樹脂に溶解させるために、ジメチルスルフォキシドやジメチルホルムアミド等の極性の高い高沸点有機溶剤を併用しなければならないと云う問題点があった。
【０００７】
このような問題点を解決するために、特開２００１−１１０５７号公報にはイソシアヌル環に結合している２−カルボキシエチル基の代わりに２−カルボキシプロピル基を置換させたイソシアヌレート化合物が提案されている。
【０００８】
また、特開２０００−６３４８９号公報には、ＣＩＣ酸のフェノールエステル化合物が、同２０００−３１９２６７号公報には、ＣＩＣ酸とビニルエーテル化合物とを反応させて得られるイソシアヌレート化合物が各々提案されている。
【０００９】
【発明が解決しようとする課題】
この発明は、ＣＩＣ酸が発揮し得る優れた硬化特性を維持しながら、ＣＩＣ酸が高融点であって、且つエポキシ樹脂に対する溶解性が低いことに由来する問題点、即ちエポキシ樹脂の硬化に２００℃以上の高温を必要とすると云う問題点あるいは１５０℃程度の比較的低い温度で硬化させるためには、極性が高い高沸点の溶剤を配合しなければならないと云う問題点を解決することを目的とする。
【００１０】
【課題を解決するための手段】
本発明者等は、前記の課題を解決するために鋭意研究を重ねた結果、ＣＩＣ酸のｔ−ブチルエステル化合物が、所期の目的を達成し得ることを見出し、本発明を完成するに至ったものである。
すなわち、本発明は化２で示されるイソシアヌル酸環を有する新規なエステル化合物及び、該化合物を硬化剤として配合したことを特徴とするエポキシ樹脂組成物に関する。
【００１１】
【化２】
【発明の実施の形態】
以下、本発明を詳細に説明する。
化２で示される本化合物の１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートは、下記のＡ工程およびＢ工程を経ることで製造できる。
【００１３】
Ａ工程：ＣＩＣ酸を塩化チオニルと反応させて、化３で表される１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレートを製造する工程。
【００１４】
【化３】
Ｂ工程：前記の１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレートとｔ−ブチルアルコールを反応させる工程。
【００１６】
Ａ工程の反応は、ＣＩＣ酸１モルに対して、塩化チオニルを３〜５モル用い、Ｎ，Ｎ−ジメチルホルムアミド等の溶媒中で、６０℃以下の反応温度、１〜２時間の反応時間で行うことができる。
【００１７】
続いてＢ工程の反応は、Ａ工程で得られた１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレート１モルに対して、ｔ−ブチルアルコールを３〜５モル用い、ピリジン等の塩基性化合物を３モル加え、クロロホルム等の不活性溶媒中で、６０〜７０℃の温度で１〜５時間の反応時間で行うことができる。
【００１８】
このようにして得られた１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートは、イソプロピルアルコール、酢酸エチル等の低沸点溶媒に可溶な１１５〜１２０℃の融点を有する白色の結晶である。
【００１９】
本発明の１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートをエポキシ樹脂の硬化剤として使用する場合、一分子内に平均して２個以上のエポキシ基を有するエポキシ樹脂に対して、１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートを、エポキシ基／エステル基の当量比で０．５〜４．０の割合で配合し、また必要に応じてイミダゾール類、トリフェニルホスフィン等の三価のリン化合物、三級アミン類および四級アンモニウム塩や四級ホスホニウム塩等の第四オニウム塩等から選ばれる１種類または２種類以上を混合したものを硬化促進剤として、エポキシ樹脂１００重量部に対して０．１〜１０重量部の割合で添加することができる。
【００２０】
本発明で使用するエポキシ樹脂は、特に限定されるものではなく平均して一分子内に２個以上のエポキシ基を有するものであれば良い。
代表的なエポキシ樹脂としては、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、ビスフェノールＡＤ型エポキシ樹脂、ヒダントイン型を有するエポキシ樹脂、トリグリシジルイソシアヌレート、カテコールやレゾルシノール等の多価フェノールまたはグリセリン、ポリエチレングリコール等の多価アルコールとエピクロルヒドリンを反応させて得られるグリシジルエーテル、フタル酸またはイソフタル酸のようなポリカルボン酸とエピクロルヒドリンを反応させて得られるポリグリシジルエステル、更にはエポキシ化フェノールノボラック樹脂、エポキシ化ポリオレフィン、水溶性エポキシ樹脂、その他ウレタン変性エポキシ樹脂等が挙げられるが、これらに限定されるものではない。
【００２１】
本発明のエポキシ樹脂組成物には、必要に応じて希釈剤、可撓性付与剤、シラン系カップリング剤、消泡剤、レベリング剤、充填剤、顔料、染料等の各種添加剤を加えることができる。
【００２２】
【実施例】
以下、実施例および比較例によって本発明を詳細に説明するが、本発明はこれらの実施例に制限されるものではない。
なお、実施例および比較例における評価試験は、次に示した試験規格および条件によって行ったものである。
【００２３】
［評価試験方法］
▲１▼エポキシ樹脂の硬化性
・ゲル化時間：ＪＩＳ Ｃ−２１０５〔熱板法（１５０℃）〕
・ポットライフ：ＪＩＳ Ｋ−６８３８〔初期粘度の２倍に達する時間〕
▲２▼硬化物の外観：目視
▲３▼エポキシ樹脂硬化塗膜の物性
・耐屈曲性：ＪＩＳ Ｋ−５４００〔折り曲げ試験、測定温度２５℃〕
・密着性：ＪＩＳ Ｋ−５４００〔碁盤目試験、測定温度２５℃〕
・硬さ：ＪＩＳ Ｋ−５４００〔鉛筆引っかき試験、測定温度２５℃〕
【００２４】
〔実施例１〕
＜１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレートの合成＞攪拌機、温度計および冷却管を備えたフラスコに、Ｎ，Ｎ−ジメチルホルムアミド１４０ｍｌを仕込み、ＣＩＣ酸５５．２４ｇ（０．１６０モル）を加え、室温で攪拌しながら溶解させた。次いで、攪拌下塩化チオニル４０．６ｍｌ（０．５２８モル）を１時間で滴下した。この間液温は２６℃から５８℃まで上昇し、滴下途中で白色結晶が析出し始め、滴下終了時には反応液がスラリー状になった。
滴下終了後、さらに室温で１時間攪拌を続け、その後冷却し析出した結晶を濾取し、クロロホルム５０ｍｌで洗浄してエバポレータで乾燥することにより、１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレート５９．８７ｇを得た。原料であるＣＩＣ酸に対する収率は９３．４％であった。
【００２５】
得られた化合物のスペクトルデータは以下のとおりであった。
ＩＲ（ＫＢｒ法）／ν（ｃｍ−１）
１８１５，１７９６ Ｃ＝Ｏ伸縮
１４６２ イソシアヌル酸環
【００２６】
＜１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートの合成＞
攪拌機、温度計および冷却管を備えたフラスコに、クロロホルム１００ｍｌ、ｔ−ブタノール２５．０ｇ（０．３３１モル）およびピリジン２５ｍｌ（０．３０６モル）を仕込み、攪拌して均一な溶液にした。次いで攪拌を行いながら、前記１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレート４０．０６ｇ（０．１００モル）を１時間かけて添加した。この間液温は２５℃から３０℃に上昇した。添加終了後、さらに６５℃で１時間反応させた。
反応終了後、反応液を濃縮し、濃縮物にクロロホルム７０ｍｌを加えて、水５０ｍｌで洗浄した。クロロホルム相を分取し、硫酸マグネシウムで乾燥させた後、濃縮して乳白色の結晶を得た。この結晶をメタノールから再結晶させて１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレート３１．８ｇを得た。原料である１，３，５−トリス（２−クロロホルミルエチル）イソシアヌレートに対する収率は６１．９％であった。
得られた化合物の性状、融点、スペクトルデータは表１に示したとおりであった。
【００２７】
【表１】
〔実施例２〕
エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、油化シェルエポキシ社製、商品名「エピコート８２８」、エポキシ当量１８６）と、硬化剤として実施例１で得られた１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートをエポキシ基／エステル基の当量比が１：１になる割合で配合し、更に硬化促進剤として２−フェニルイミダゾールをエポキシ樹脂１００重量部に対して４重量部の割合で添加した後、乳鉢で粉砕・混合し、均一に分散したエポキシ樹脂組成物を調製した。
【００２９】
得られたエポキシ樹脂組成物について、１５０℃におけるエポキシ樹脂の硬化性（ゲル化時間）、２５℃における保存安定性（ポットライフ）を評価した結果は、表２に示したとおりであった。
また、得られたエポキシ樹脂組成物を、アルミ板の表面に刷毛で均一に塗り、１５０℃のオーブンを用いて３０分間加熱硬化させ、得られた塗膜の外観を目視にて確認した。次いでアルミ板を所定の寸法に切り出し、塗膜の物性（耐屈曲性、密着性、硬さ）を調べたところ、これらの結果は表２に示したとおりであった。
なお、アルミ板の場合と同様にして、前記エポキシ樹脂組成物を銅板の表面に塗布し、塗膜の外観および物性を評価したところ、材質の違いによる塗膜の外観および物性の差は認められなかった。
【００３０】
〔比較例１〕
エポキシ樹脂およびＣＩＣ酸をエポキシ基／カルボキシル基の当量比が１：１になる割合で配合し、乳鉢で粉砕・混合し、均一に分散したエポキシ樹脂組成物を調製した。得られた組成物について、実施例２と同様にして各種評価試験を行ったところ、これらの試験結果は、表２に示したとおりであった。
【００３１】
〔比較例２〕
エポキシ樹脂およびＣＩＣ酸をエポキシ基／カルボキシル基の当量比が１：１になる割合で配合し、さらに２−フェニルイミダゾールをエポキシ樹脂１００重量部に対して４重量部の割合で添加した後、乳鉢で粉砕・混合し、均一に分散した樹脂組成物を調製した。得られた組成物について、実施例２と同様にして各種評価試験を行ったところ、これらの試験結果は、表２に示したとおりであった。
【００３２】
【表２】
実施例２と比較例２を比べると、本発明の１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートを配合したエポキシ樹脂組成物の硬化物は、ＣＩＣ酸を配合した場合よりもゲル化時間が短くなっているので硬化性が優れ、またポットライフが著しく長くなっており、保存安定性が飛躍的に改善されているものと認められる。
また、エポキシ樹脂硬化塗膜についても、透明で均質なものであり、耐屈曲性および密着性に優れ、硬度も高く優れた物性を有しているものと認められる。
【００３４】
【発明の効果】
本発明の１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートは、ＣＩＣ酸と比較して融点が低く、有機溶剤に対する溶解性およびエポキシ樹脂への相溶性が良好である。また、本発明の１，３，５−トリス〔２−（ｔ−ブトキシカルボニル）エチル〕イソシアヌレートを硬化剤に使用したエポキシ樹脂組成物は、硬化性および常温における保存安定性が良好であって、且つ透明で金属への密着性に優れた硬化物を与えるので、塗料、接着剤などの分野において好適なものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel ester compound having an isocyanuric acid ring useful as a curing agent for an epoxy resin, and an epoxy resin composition containing the compound.
[0002]
[Prior art]
Epoxy resin compositions can exhibit excellent electrical, mechanical, and thermal properties by combining various types of epoxy resins with curing agents and, if necessary, curing accelerators. Used in
[0003]
As a curing agent for an epoxy resin, an acid compound such as an acid anhydride and a phenol compound, and a basic compound such as an amine, urea, and imidazole are generally used depending on the properties required of the cured product. .
[0004]
An epoxy resin composition in which 1,3,5-tris (2-carboxyethyl) isocyanurate (hereinafter referred to as CIC acid), which is one of acidic compounds, is blended as a curing agent has been proposed (for example, Japanese Patent Application Laid-open No. 59-107742, JP-A-8-506134, JP-A-11-293187, JP-A-11-293189, JP-A-2001-502003, etc.).
[0005]
However, when CIC acid is used as a curing agent for an epoxy resin, the CIC acid has a high melting point (223 to 226 ° C.) and poor compatibility with the epoxy resin. There is a disadvantage that the above-mentioned high curing temperature is required.
That is, at a curing temperature of less than 200 ° C., the curing reaction is not completed because the CIC acid added to the epoxy resin remains in a solid state, and it is a matter of course that various properties of the obtained cured product are poor. Since the CIC acid remains, the cured product becomes opaque and its appearance is poor.
[0006]
On the other hand, in order to cure at a relatively low temperature of about 150 ° C., a highly polar high-boiling organic solvent such as dimethyl sulfoxide or dimethylformamide must be used in combination to dissolve the CIC acid in the epoxy resin. There was a problem called.
[0007]
In order to solve such problems, JP-A-2001-11057 proposes an isocyanurate compound in which a 2-carboxypropyl group is substituted for a 2-carboxyethyl group bonded to an isocyanuric ring. ing.
[0008]
JP-A-2000-63489 proposes a phenol ester compound of CIC acid, and JP-A-2000-319267 proposes an isocyanurate compound obtained by reacting a CIC acid with a vinyl ether compound. .
[0009]
[Problems to be solved by the invention]
This invention solves the problems derived from the fact that the CIC acid has a high melting point and low solubility in the epoxy resin while maintaining the excellent curing properties that the CIC acid can exhibit, that is, a problem of curing the epoxy resin by 200 times. The object of the present invention is to solve the problem that a high temperature of not less than 150 ° C. is required or the problem that a solvent having a high polarity and a high boiling point must be added in order to cure at a relatively low temperature of about 150 ° C. And
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a t-butyl ester compound of CIC acid can achieve the intended purpose, and have completed the present invention. It is a thing.
That is, the present invention relates to a novel ester compound having an isocyanuric acid ring represented by Chemical formula 2, and an epoxy resin composition characterized by blending the compound as a curing agent.
[0011]
Embedded image
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
1,3,5-Tris [2- (t-butoxycarbonyl) ethyl] isocyanurate of the present compound represented by Chemical formula 2 can be produced through the following steps A and B.
[0013]
Step A: a step of reacting the CIC acid with thionyl chloride to produce 1,3,5-tris (2-chloroformylethyl) isocyanurate represented by Chemical Formula 3.
[0014]
Embedded image
Step B: a step of reacting the above 1,3,5-tris (2-chloroformylethyl) isocyanurate with t-butyl alcohol.
[0016]
In the reaction of the step A, 3 to 5 mol of thionyl chloride is used per 1 mol of CIC acid in a solvent such as N, N-dimethylformamide at a reaction temperature of 60 ° C. or lower and a reaction time of 1 to 2 hours. It can be carried out.
[0017]
Subsequently, in the reaction of the step B, 3 to 5 mol of t-butyl alcohol is used for 1 mol of 1,3,5-tris (2-chloroformylethyl) isocyanurate obtained in the step A, and pyridine or the like is used. The reaction can be carried out in an inert solvent such as chloroform at a temperature of 60 to 70 ° C. for 1 to 5 hours in 3 mol of a basic compound.
[0018]
1,3,5-Tris [2- (t-butoxycarbonyl) ethyl] isocyanurate thus obtained has a melting point of 115 to 120 ° C. which is soluble in a low boiling point solvent such as isopropyl alcohol and ethyl acetate. White crystals.
[0019]
When the 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate of the present invention is used as a curing agent for an epoxy resin, an epoxy having two or more epoxy groups on average in one molecule. 1,3,5-Tris [2- (t-butoxycarbonyl) ethyl] isocyanurate is blended with the resin at an equivalent ratio of epoxy group / ester group of 0.5 to 4.0, and Mix one or more selected from trivalent phosphorus compounds such as imidazoles and triphenylphosphine, tertiary amines and quaternary onium salts such as quaternary ammonium salts and quaternary phosphonium salts, if necessary. The cured product can be added as a curing accelerator at a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin.
[0020]
The epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule on average.
Representative epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, epoxy resin having hydantoin type, triglycidyl isocyanurate, polyhydric phenol such as catechol and resorcinol, glycerin, and polyethylene. Glycidyl ether obtained by reacting a polyhydric alcohol such as glycol with epichlorohydrin, polyglycidyl ester obtained by reacting a polycarboxylic acid such as phthalic acid or isophthalic acid with epichlorohydrin, and further epoxidized phenol novolak resin, epoxidation Examples include polyolefins, water-soluble epoxy resins, and other urethane-modified epoxy resins, but are not limited thereto.
[0021]
To the epoxy resin composition of the present invention, if necessary, various additives such as a diluent, a flexibility-imparting agent, a silane-based coupling agent, an antifoaming agent, a leveling agent, a filler, a pigment, and a dye may be added. Can be.
[0022]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The evaluation tests in Examples and Comparative Examples were performed according to the following test standards and conditions.
[0023]
[Evaluation test method]
{Circle around (1)} Curability and gel time of epoxy resin: JIS C-2105 [Hot plate method (150 ° C)]
・ Pot life: JIS K-6838 [Time to reach twice the initial viscosity]
(2) Appearance of cured product: visual (3) Physical properties and flex resistance of epoxy resin cured coating: JIS K-5400 [Bending test, measurement temperature 25 ° C]
・ Adhesion: JIS K-5400 [crosscut test, measurement temperature 25 ° C]
・ Hardness: JIS K-5400 [pencil scratch test, measurement temperature 25 ° C]
[0024]
[Example 1]
<Synthesis of 1,3,5-tris (2-chloroformylethyl) isocyanurate> 140 ml of N, N-dimethylformamide was charged into a flask equipped with a stirrer, a thermometer and a condenser, and 55.24 g of CIC acid (0 .160 mol) and dissolved at room temperature with stirring. Then, 40.6 ml (0.528 mol) of thionyl chloride was added dropwise with stirring over 1 hour. During this time, the liquid temperature rose from 26 ° C. to 58 ° C., and white crystals began to precipitate in the course of dropping, and the reaction liquid became a slurry at the end of dropping.
After completion of the dropwise addition, stirring was further continued at room temperature for 1 hour, followed by cooling. The precipitated crystals were collected by filtration, washed with 50 ml of chloroform and dried by an evaporator to give 1,3,5-tris (2-chloroformylethyl). ) 59.87 g of isocyanurate were obtained. The yield based on the starting material CIC acid was 93.4%.
[0025]
The spectral data of the obtained compound were as follows.
IR (KBr method) / ν (cm −1 )
1815, 1796 C = O stretching 1462 isocyanuric acid ring
<Synthesis of 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate>
A flask equipped with a stirrer, thermometer and condenser was charged with 100 ml of chloroform, 25.0 g (0.331 mol) of t-butanol and 25 ml (0.306 mol) of pyridine and stirred to form a uniform solution. Then, while stirring, 40.06 g (0.100 mol) of the above 1,3,5-tris (2-chloroformylethyl) isocyanurate was added over 1 hour. During this time, the liquid temperature rose from 25 ° C to 30 ° C. After the addition was completed, the reaction was further performed at 65 ° C. for 1 hour.
After completion of the reaction, the reaction solution was concentrated, 70 ml of chloroform was added to the concentrate, and the mixture was washed with 50 ml of water. The chloroform phase was separated, dried over magnesium sulfate, and concentrated to obtain milky white crystals. The crystals were recrystallized from methanol to obtain 31.8 g of 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate. The yield based on 1,3,5-tris (2-chloroformylethyl) isocyanurate as a raw material was 61.9%.
The properties, melting point and spectrum data of the obtained compound were as shown in Table 1.
[0027]
[Table 1]
[Example 2]
An epoxy resin (bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., trade name “Epicoat 828”, epoxy equivalent 186), and 1,3,5-tris [2- ( [t-butoxycarbonyl) ethyl] isocyanurate in a ratio of 1: 1 equivalent ratio of epoxy group / ester group, and 2-phenylimidazole as a curing accelerator at 4 parts by weight based on 100 parts by weight of epoxy resin. And then pulverized and mixed in a mortar to prepare a uniformly dispersed epoxy resin composition.
[0029]
The results of evaluating the curability (gel time) of the epoxy resin at 150 ° C. and the storage stability (pot life) at 25 ° C. of the obtained epoxy resin composition are as shown in Table 2.
The obtained epoxy resin composition was evenly applied to the surface of an aluminum plate with a brush, and was heated and cured in an oven at 150 ° C. for 30 minutes, and the appearance of the obtained coating film was visually observed. Next, the aluminum plate was cut out to a predetermined size, and the physical properties (bending resistance, adhesion, hardness) of the coating film were examined. The results are as shown in Table 2.
Incidentally, in the same manner as in the case of the aluminum plate, the epoxy resin composition was applied to the surface of the copper plate, and the appearance and physical properties of the coating film were evaluated. Did not.
[0030]
[Comparative Example 1]
The epoxy resin and the CIC acid were blended at a ratio of an epoxy group / carboxyl group equivalent of 1: 1 and ground and mixed in a mortar to prepare a uniformly dispersed epoxy resin composition. Various evaluation tests were performed on the obtained composition in the same manner as in Example 2. The results of these tests were as shown in Table 2.
[0031]
[Comparative Example 2]
An epoxy resin and a CIC acid are blended at a ratio of an epoxy group / carboxyl group equivalent ratio of 1: 1. Further, 2-phenylimidazole is added at a ratio of 4 parts by weight with respect to 100 parts by weight of the epoxy resin. To prepare a uniformly dispersed resin composition. Various evaluation tests were performed on the obtained composition in the same manner as in Example 2. The results of these tests were as shown in Table 2.
[0032]
[Table 2]
Comparing Example 2 with Comparative Example 2, the cured product of the epoxy resin composition containing 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate of the present invention contains CIC acid. Since the gelation time is shorter than in the case where the curing was carried out, the curability is excellent, and the pot life is remarkably increased, so that it is recognized that the storage stability is dramatically improved.
The epoxy resin cured film is also transparent and homogeneous, and has excellent flex resistance and adhesiveness, high hardness, and excellent physical properties.
[0034]
【The invention's effect】
The 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate of the present invention has a lower melting point than CIC acid, and has good solubility in organic solvents and good compatibility with epoxy resins. is there. The epoxy resin composition of the present invention using 1,3,5-tris [2- (t-butoxycarbonyl) ethyl] isocyanurate as a curing agent has good curability and storage stability at room temperature. In addition, since it gives a cured product which is transparent and has excellent adhesion to metal, it is suitable in the fields of paints and adhesives.
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| JP2002175002A JP4181797B2 (en) | 2002-06-14 | 2002-06-14 | Novel ester compound having isocyanuric acid ring and epoxy resin composition using the compound |
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| JP2002175002A JP4181797B2 (en) | 2002-06-14 | 2002-06-14 | Novel ester compound having isocyanuric acid ring and epoxy resin composition using the compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012025670A (en) * | 2010-07-20 | 2012-02-09 | Shikoku Chem Corp | Isocyanurate compound |
| WO2019009097A1 (en) * | 2017-07-03 | 2019-01-10 | 株式会社弘輝 | Flux and soldering material |
| WO2019142826A1 (en) * | 2018-01-16 | 2019-07-25 | 千住金属工業株式会社 | Flux and solder paste |
| JP2020110833A (en) * | 2019-01-15 | 2020-07-27 | 千住金属工業株式会社 | Flux and solder paste |
| JP2020110832A (en) * | 2019-01-15 | 2020-07-27 | 千住金属工業株式会社 | Flux and solder paste |
| JP7408591B2 (en) | 2021-03-22 | 2024-01-05 | 四国化成工業株式会社 | Isocyanurate compound having a carboxyl group and epoxy resin composition using the compound |
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- 2002-06-14 JP JP2002175002A patent/JP4181797B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012025670A (en) * | 2010-07-20 | 2012-02-09 | Shikoku Chem Corp | Isocyanurate compound |
| US10864606B2 (en) | 2017-07-03 | 2020-12-15 | Koki Company Limited | Flux and solder material |
| WO2019009097A1 (en) * | 2017-07-03 | 2019-01-10 | 株式会社弘輝 | Flux and soldering material |
| JP2019013926A (en) * | 2017-07-03 | 2019-01-31 | 株式会社弘輝 | Flux and solder material |
| CN109429491A (en) * | 2017-07-03 | 2019-03-05 | 株式会社弘辉 | Scaling powder and welding material |
| EP3741498A4 (en) * | 2018-01-16 | 2021-10-13 | Senju Metal Industry Co., Ltd | Flux and solder paste |
| WO2019142826A1 (en) * | 2018-01-16 | 2019-07-25 | 千住金属工業株式会社 | Flux and solder paste |
| EP4063061A1 (en) * | 2018-01-16 | 2022-09-28 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
| EP4063060A1 (en) * | 2018-01-16 | 2022-09-28 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
| US11833620B2 (en) | 2018-01-16 | 2023-12-05 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
| JP2020110832A (en) * | 2019-01-15 | 2020-07-27 | 千住金属工業株式会社 | Flux and solder paste |
| JP2020110833A (en) * | 2019-01-15 | 2020-07-27 | 千住金属工業株式会社 | Flux and solder paste |
| JP2021102232A (en) * | 2019-01-15 | 2021-07-15 | 千住金属工業株式会社 | Flux and solder paste |
| JP7408591B2 (en) | 2021-03-22 | 2024-01-05 | 四国化成工業株式会社 | Isocyanurate compound having a carboxyl group and epoxy resin composition using the compound |
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