JP3377812B2 - New polymerizable monomer - Google Patents
New polymerizable monomerInfo
- Publication number
- JP3377812B2 JP3377812B2 JP30884492A JP30884492A JP3377812B2 JP 3377812 B2 JP3377812 B2 JP 3377812B2 JP 30884492 A JP30884492 A JP 30884492A JP 30884492 A JP30884492 A JP 30884492A JP 3377812 B2 JP3377812 B2 JP 3377812B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- formula
- polymerizable monomer
- embedded image
- acrylate
- 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
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、光及び熱硬化樹脂、塗
料、接着剤、インキ等の原料として有用な、新規な重合
性単量体に関するものである。
【０００２】
【従来の技術】光及び熱硬化樹脂、塗料、接着剤、イン
キ等の原料としては、柔軟性、強靱性などが優れている
ことから、ウレタンアクリレートが広く使用されてい
る。しかしながら、ウレタンアクリレートの原料である
トリレンジイソシアネートや、4,4 −ジフェニルメタン
ジイソシアネート等は黄変性があるため、これらを用い
たウレタンアクリレートも透明な樹脂、塗料、接着剤な
どへの利用はできない。
【０００３】
【発明が解決しようとする課題】本発明の目的は、透明
な樹脂、塗料、接着剤等に使用でき、しかも、黄変性の
ないウレタンアクリレートである新規な重合性単量体を
提供することである。
【０００４】
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を行った。その結果、ビシクロ環
を有する新規な重合性単量体を見出した。すなわち、本
発明は、一般式（Ｉ）（化２）で表される重合性単量体
に関するものである。
【０００５】
【化２】
本発明の重合性単量体としては、具体的には、下記の構
造式（化３）で示される化合物が挙げられる。
【０００６】
【化３】【０００７】これらの化合物は、ノルボルネンジイソシ
アネート（NBDI）と、２−ヒドロキシエチル（メタ）ア
クリレート、２−ヒドロキシプロピルアクリレート、２
−ヒドロキシ− 1,3−ジ（メタ）アクリロイルオキシプ
ロパン、２−ヒドロキシ−３−アクリロイルオキシプロ
ピルメタクリレート等のアクリレート化合物とを、無溶
媒または溶媒中で反応させて得られるものである。溶媒
としては、原料類と反応性を有しない溶媒であり、例え
ば、ヘキサン、クロロホルム、ベンゼン、トルエン等が
用いられる。
【０００８】反応の際のNBDIとアクリレート化合物との
割合は、NBDI１モルに対し、アクリレート化合物 1.8〜
2.2モル、好ましくは 1.9〜 2.1モルである。反応は、
NBDIあるいはNBDIと溶媒の混合液にアクリレート化合物
を滴下し、無触媒で、またはジブチルスズジラウレート
などのウレタン化促進触媒の存在下に反応させる。反応
温度は30〜90℃、好ましくは40〜70℃である。ウレタン
化促進触媒の使用量は、イソシアネート重量に対し、0.
01〜５重量％、好ましくは 0.1〜１重量％である。反応
終了後、反応液は、カラムクロマトグラフィー等により
精製することにより、本発明の重合性モノマーを得るこ
とができる。
【０００９】
【実施例】以下、実施例により本発明を詳しく説明する
が、本発明はこの実施例によって何等限定されるもので
はない。実施例中の部は重量部を表す。
実施例１
ノルボルネンジイソシアネート20.6部、トルエン30部、
ジブチルスズジラウレート 0.1部を混合し、反応温度を
50℃に保ちながら、２−ヒドロキシエチルアクリレート
23.2部を30分かけて滴下し、さらに１時間攪拌して反応
を行った。反応終了後、反応液を濃縮した。濃縮液はク
ロマトグラフ法により精製し、無色透明な下記構造式
（化４）で示される単量体41.4部を得た。なお、 1Ｈ−
ＮＭＲは下記（化５）の通りであった。
【００１０】
【化４】
【００１１】
【化５】
【００１２】実施例２
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシプロピルアクリレート26.0部に代え
る以外は、実施例１と同様にして、下記構造式（化６）
で示される単量体46.9部を得た。なお、 1Ｈ−ＮＭＲは
下記（化７）の通りであった。
【００１３】
【化６】
【００１４】
【化７】【００１５】実施例３
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシエチルメタアクリレート26.0部に代
える以外は、実施例１と同様にして、下記構造式（化
８）で示される単量体46.2部を得た。なお、 1Ｈ−ＮＭ
Ｒは下記（化９）の通りであった。
【００１６】
【化８】
【００１７】
【化９】【００１８】実施例4
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシプロピルメタクリレート28.8部に代
える以外は、実施例１と同様にして、下記構造式（化１
０）で示される単量体49.8部を得た。なお、 1Ｈ−ＮＭ
Ｒは下記（化１１）の通りであった。
【００１９】
【化１０】
【００２０】
【化１１】【００２１】実施例５
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシ− 1,3−ジアクリロイルオキシプロ
パン40.0部に代える以外は、実施例１と同様にして、下
記構造式（化１２）で示される単量体61.4部を得た。な
お、 1Ｈ−ＮＭＲは下記（化１３）の通りであった。
【００２２】
【化１２】
【００２３】
【化１３】【００２４】実施例６
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシ− 1,3−ジメタアクリロイルオキシ
プロパン45.6部に代える以外は、実施例１と同様にし
て、下記構造式（化１４）で示される単量体66.3部を得
た。なお、 1Ｈ−ＮＭＲは下記（化１５）の通りであっ
た。
【００２５】
【化１４】
【００２６】
【化１５】【００２７】実施例７
実施例１の２−ヒドロキシエチルアクリレート23.2部
を、２−ヒドロキシ−３−アクリロイルオキシプロピル
メタクリレート42.8部に代える以外は、実施例１と同様
にして、下記構造式（化１６）で示される単量体63.3部
を得た。なお、 1Ｈ−ＮＭＲは下記（化１７）の通りで
あった。
【００２８】
【化１６】
【００２９】
【化１７】【００３０】参考例１
実施例１の単量体５０部に１，６−ヘキサンジオールジ
アクリレート１０部、ｔ−ブチルパーオキシ−２−エチ
ルヘキサノエート０．１部を溶解混合し、濾過、脱泡
後、２枚の板ガラスと塩化ビニールのガスケットで構成
されたモールドに注入し、４０℃から１００℃まで、２
４時間かけて昇温して重合を行った。その後、冷却し、
モールドから離型して、表面が平滑で、透明な３mm厚の
樹脂板を得た。この樹脂板の光線透過率は８９％であ
り、鉛筆硬度（ JIS-K-5400 法による) は２Ｈであり、
耐薬品性（イソプロパノールおよびトルエンに、室温で
２４時間浸漬後、ＨＢの鉛筆で引っかき傷の出来ないも
のを良好とする）が良好で、金切ノコギリによる切断が
可能であった。さらに、この板をサンシャインウェザロ
メーター（ JIS-B-7753 による) にて100 時間暴露後、
色相の変化を目視にて観察したが、変化は認められなか
った。
【００３１】
【発明の効果】本発明の新規重合性モノマーを用いた樹
脂は、柔軟性、強靱性に優れ、かつ耐黄変性を有してい
ることから、光学用樹脂等の透明樹脂、透明な塗料、接
着剤、インク等の原料に適している。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerizable monomer useful as a raw material for light and thermosetting resins, paints, adhesives, inks and the like. is there. 2. Description of the Related Art Urethane acrylate is widely used as a raw material for light and thermosetting resins, paints, adhesives, inks, etc. because of its excellent flexibility and toughness. However, urethane acrylate raw materials such as tolylene diisocyanate and 4,4-diphenylmethane diisocyanate have yellowing properties, so that urethane acrylates using these materials cannot be used for transparent resins, paints, adhesives and the like. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polymerizable monomer which can be used for transparent resins, paints, adhesives and the like, and which is a urethane acrylate free from yellowing. It is to be. [0004] The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, a novel polymerizable monomer having a bicyclo ring was found. That is, the present invention relates to a polymerizable monomer represented by the general formula (I) (Formula 2). [0005] Specific examples of the polymerizable monomer of the present invention include compounds represented by the following structural formula (Formula 3). [0006] These compounds include norbornene diisocyanate (NBDI), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate,
-Hydroxy-1,3-di (meth) acryloyloxypropane, 2-hydroxy-3-acryloyloxypropyl methacrylate, and other acrylate compounds obtained by reacting with or without a solvent. The solvent is a solvent having no reactivity with the raw materials, and for example, hexane, chloroform, benzene, toluene and the like are used. In the reaction, the ratio of NBDI to the acrylate compound is from 1.8 to acrylate compound to 1 mole of NBDI.
It is 2.2 mol, preferably 1.9 to 2.1 mol. The reaction is
An acrylate compound is added dropwise to NBDI or a mixture of NBDI and a solvent, and the reaction is carried out without a catalyst or in the presence of a urethanization-promoting catalyst such as dibutyltin dilaurate. The reaction temperature is 30 to 90 ° C, preferably 40 to 70 ° C. The amount of the urethane-promoting catalyst used is 0.
It is from 0.01 to 5% by weight, preferably from 0.1 to 1% by weight. After completion of the reaction, the reaction solution is purified by column chromatography or the like to obtain the polymerizable monomer of the present invention. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts in the examples represent parts by weight. Example 1 20.6 parts of norbornene diisocyanate, 30 parts of toluene,
Mix 0.1 part of dibutyltin dilaurate and lower the reaction temperature.
While maintaining at 50 ° C, add 2-hydroxyethyl acrylate
23.2 parts were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour to carry out a reaction. After completion of the reaction, the reaction solution was concentrated. The concentrate was purified by chromatography to obtain 41.4 parts of a colorless and transparent monomer represented by the following structural formula (Formula 4). Note that 1 H−
NMR was as shown in the following (Chemical Formula 5). [0010] [0011] Example 2 The procedure of Example 1 was repeated, except that 23.2 parts of 2-hydroxyethyl acrylate was replaced by 26.0 parts of 2-hydroxypropyl acrylate.
46.9 parts of a monomer represented by the following formula: were obtained. In addition, 1 H-NMR was as follows (Chemical formula 7). [0013] Embedded image Example 3 In the same manner as in Example 1 except that 23.2 parts of 2-hydroxyethyl acrylate in Example 1 was replaced with 26.0 parts of 2-hydroxyethyl methacrylate, the compound was represented by the following structural formula (Formula 8). 46.2 parts of a monomer were obtained. Note that 1 H-NM
R was as shown below. Embedded image Embedded image Example 4 The following structural formula was prepared in the same manner as in Example 1 except that 23.2 parts of 2-hydroxyethyl acrylate in Example 1 was replaced with 28.8 parts of 2-hydroxypropyl methacrylate.
49.8 parts of a monomer represented by the formula (0) were obtained. Note that 1 H-NM
R was as shown below. Embedded image Embedded image Example 5 The same procedure as in Example 1 was carried out except that 23.2 parts of 2-hydroxyethyl acrylate in Example 1 was replaced with 40.0 parts of 2-hydroxy-1,3-diacryloyloxypropane. 61.4 parts of a monomer represented by the formula 12) were obtained. In addition, < 1 > H-NMR was as follows (Formula 13). Embedded image Embedded image Example 6 The following structural formula was prepared in the same manner as in Example 1 except that 23.2 parts of 2-hydroxyethyl acrylate in Example 1 was replaced with 45.6 parts of 2-hydroxy-1,3-dimethacryloyloxypropane. 66.3 parts of a monomer represented by the following formula (14) were obtained. In addition, 1 H-NMR was as follows (Chemical Formula 15). Embedded image Embedded image Example 7 In the same manner as in Example 1 except that 23.2 parts of 2-hydroxyethyl acrylate in Example 1 was replaced with 42.8 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate, the following structural formula (Chemical Formula 16) was used. 63.3 parts of a monomer represented by the formula (1) was obtained. In addition, 1 H-NMR was as follows (Formula 17). Embedded image Embedded image Reference Example 1 In 50 parts of the monomer of Example 1, 10 parts of 1,6-hexanediol diacrylate and 0.1 part of t-butylperoxy-2-ethylhexanoate were dissolved and mixed. After defoaming, it is poured into a mold composed of two glass sheets and a gasket of vinyl chloride.
The polymerization was carried out by raising the temperature over 4 hours. Then cool down,
After releasing from the mold, a transparent resin plate having a smooth surface and a thickness of 3 mm was obtained. The light transmittance of this resin plate is 89%, the pencil hardness (according to JIS-K-5400 method) is 2H,
Good chemical resistance (after immersion in isopropanol and toluene at room temperature for 24 hours, and those which can not be scratched with HB pencils are good), and cutting with a slicing saw was possible. After exposing this plate for 100 hours with a sunshine weatherometer (according to JIS-B-7753),
A change in hue was visually observed, but no change was observed. The resin using the novel polymerizable monomer of the present invention is excellent in flexibility and toughness and has yellowing resistance. Suitable for raw materials such as paints, adhesives and inks.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−83562（ＪＰ，Ａ) 特開 平４−226965（ＪＰ，Ａ) 特開 平３−290420（ＪＰ，Ａ) 特開 平１−213601（ＪＰ，Ａ) 特開 昭63−183905（ＪＰ，Ａ) 特開 昭61−97253（ＪＰ，Ａ) 特開 平４−33969（ＪＰ，Ａ) 特開 平４−85319（ＪＰ，Ａ) 特開 平４−85320（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 271/20 C08F 20/36 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-57-83562 (JP, A) JP-A-4-226965 (JP, A) JP-A-3-290420 (JP, A) JP-A-1- 213601 (JP, A) JP-A-63-183905 (JP, A) JP-A-61-97253 (JP, A) JP-A-4-33969 (JP, A) JP-A-4-85319 (JP, A) JP-A-4-85320 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 271/20 C08F 20/36 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (1)
単量体。 【化１】 (57) [Claim 1] A polymerizable monomer represented by the general formula (I) (Formula 1). Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30884492A JP3377812B2 (en) | 1992-11-18 | 1992-11-18 | New polymerizable monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30884492A JP3377812B2 (en) | 1992-11-18 | 1992-11-18 | New polymerizable monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157451A JPH06157451A (en) | 1994-06-03 |
| JP3377812B2 true JP3377812B2 (en) | 2003-02-17 |
Family
ID=17985963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30884492A Expired - Lifetime JP3377812B2 (en) | 1992-11-18 | 1992-11-18 | New polymerizable monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3377812B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09110947A (en) * | 1995-10-20 | 1997-04-28 | Japan Synthetic Rubber Co Ltd | Liquid curable resin composition |
| JPH11343276A (en) | 1998-03-31 | 1999-12-14 | Mitsui Chem Inc | New urethane compound and production of multifunctional aliphatic diisocyanate |
| US20070197820A1 (en) * | 2004-05-17 | 2007-08-23 | Jurgen Van Holen | Process for producing urethane (meth)acrylates and new urethane (meth)acrylates |
| CN110464657A (en) * | 2014-03-31 | 2019-11-19 | 三井化学株式会社 | Dental material uses polymerizable monomer composition as the purposes of dental material |
| US10470980B2 (en) | 2015-03-31 | 2019-11-12 | Mitsui Chemicals, Inc. | Dental polymerizable monomers, compositions, adhesive dental materials and kits |
-
1992
- 1992-11-18 JP JP30884492A patent/JP3377812B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06157451A (en) | 1994-06-03 |
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