Although many reports have been issued regarding isocyanate monomers, no attempt has been tried to

cover all isocyanate monomers as far as authors know. In this paper, we are showing the history of

isocyanate monomers that have been reported in the past, their manufacturing methods, basic

characteristics, uses, and new topics. In Consideration with the actual use as a monomer, we set

four types of isocyanate monomers as subject, MAI, TMI, IEM, and AOI, and blocked type that are

derivatives of these as well.

Specifically, in Chapter 1, the general history and properties of isocyanates will be shown.

Chapter 2 shows the history of attempts at industrial production of isocyanate monomers as far as

known as general information or to the best of author’s knowledge. Chapter 3 shows the general

properties of isocyanate monomers, mainly the properties of isocyanate unit and unsaturated groups.

Chapter 4 shows the history so far divided into three eras and explains development trends for each

era. Chapter 5 introduces newly developed materials and findings on trends as far as the authors

know.

一定架橋度のアクリル酸を5 wt% 含むアクリル酸n-ブチル-アクリル酸ランダム共重合体（ A） およびアクリル酸2 エチルヘキシル-アクリル酸ランダム共重合体（ B） について，石英ガラス板を被着体とした180° ピール試験時の糸曳きを観察した。粘着剤層厚さは15 ～60 µm，引張速度は0.017 ～5 mm·s^-1 である。ピール強度は，引張速度と粘着剤層厚さにともなって上昇した。同一粘着剤層厚さで比較すると，B ＞A であった。糸曳きのモルフォロジーは典型的な鋸歯状で，B の低引張速度，薄い粘着剤層厚さの一部で縁あり型が観察され，他は縁なし型であった。引張速度の上昇と粘着剤層厚さの低下にともなって鋸歯長さが低下し，同一引張速度での鋸歯長さはB ＞A であった。引張速度5 mm·s^-1 では，糸曳き自身が見られない場合もあったが，0.5 mm·s^-1 以下では同一引張速度での比較でピール強度と鋸歯長さに相関があった。

マイクロコーティングされたイソシアネート粒子と液状アミンを組み合せた，新しい超速硬化型一液システムを設計した。このシステムでは，硬化反応は主として，ジイソシアネートと二官能性または三官能性アミンとの間の求核的重付加に基づいた尿素結合形成である。マイクロコーティングされた4,4ʼ- ジフェニルメタンジイソシアネート（ MDI） を使用した場合，アミンとの混合物の粘度は5℃で5 週間までほとんど増加しなかったが，25℃で5 日間保存すると5 倍に上昇した。ホットプレートでのゲルタイム測定の結果，この種の熱硬化性樹脂は，40℃で25 秒，160℃で0.5 秒のような極めて短時間で硬化できることが分かった。アルミ板を用いた引張せん断試験で測定した本樹脂の接着強度は，硬化温度により8 ～26 MPa と大きく変動した。より低い温度で硬化すると，急速に硬化するイソシアネート部分が不均一系のアミンの海に十分に拡散することが非常に困難であると思われ，その結果，接着強度が低くなったと考えられる。一方，200℃で硬化した際に接着強度が25 MPa 以上となった原因は，尿素結合の解離とその後の遊離イソシアネートとアミンの完全拡散に関係していると考えられる。

In this study, to reinforce aqueous vinyl polymer solution-isocyanate adhesives（ APIs）, we mixed cellulose nanofibers（ CNFs） with two types of polyvinyl alcohol（ PVA） having different degrees of saponification and polymeric diphenylmethane diisocyanate（ pMDI） content. These adhesive mixtures were evaluated by scan ning electron microscopy（ SEM）, and their dynamic viscoelasticity, moisture absorptivity, water dissolution rate, and wood- bonding performance under compressive shear were analyzed. The partially saponified PVA showed a higher CNF reinforcement effect than the completely saponified PVA, and CNF reinforcement de creased with increasing pMDI content. In terms of dynamic viscoelasticity, the storage modulus（ E’） and loss modulus（ E’’） both were inhibited decreasing in the rubbery region above the glass transition temperature. Moisture absorptivity and water dissolution rate decreased as CNF content increased, but decreased as pMDI content increased. In contrast, wood-bonding performance declined as CNF content increased, irrespective of saponification degree and pMDI content.

The electronics industry has expanded its application area to all industries such as OA, FA, and automotive, and is growing into an important basic industry. This growth is due to continuous technological innovations such as high-density of hybrid ICs, innovated materials and new functional materials. Furthermore, it is necessary to consider strengthening regulated substances for the environment and energy saving measures recently. Silicone materials have excellent reliability and electrical properties and is used as a functional material in this area. In order for silicone adhesive to fit Green Chemistry, we are considering to avoid regulated substance such as tin based compound and energy saving due to cure condition continuously. Momentive silicones’ TN series which is one component fast moisture cure adhesives, has achieved tin-free while maintaining the same performance as the conventional TSE39x series. Also, new addition cure adhesives concept is not to require heat cure process. Conventional one component and two component addition cure adhesives TSE32x series and TSE33xx series are required >100 degC for adhesion, while new concept adhesives achieved to lower temp cure condition（<50degC or room temperature）for excellent adhesion.