JPH032448B2 - - Google Patents
Info
- Publication number
- JPH032448B2 JPH032448B2 JP60164913A JP16491385A JPH032448B2 JP H032448 B2 JPH032448 B2 JP H032448B2 JP 60164913 A JP60164913 A JP 60164913A JP 16491385 A JP16491385 A JP 16491385A JP H032448 B2 JPH032448 B2 JP H032448B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- urethane
- acrylate
- meth
- molecular weight
- 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
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Ａ 産業上の利用分野
本発明の化合物は、熱、紫外線、電子線等を用
いて、単独重合または適当な反応性モノマーと共
重合しうるものであり、塗料、インキ、接着剤、
酵母の固定化、歯科充填材等に用いられるほか、
紫外線で硬化する性質を利用し、印刷版材、フオ
トレジスト、プリント配線用レジストインキ等に
有用なラジカル重合性のウレタン（メタ）アクリ
レートに関するものである。
Ｂ 従来の技術
ラジカル重合性ウレタン（メタ）アクリレート
は、特に紫外線硬化型のプレポリマーとして利用
されることが多い。紫外線硬化型樹脂は紫外線照
射によつて液状から固形へ変化する樹脂であり、
通常、反応性プレポリマー、反応性希釈剤、光重
合開始剤から構成されている。この反応性プレポ
リマーの主流をなすのがアクリル系プレポリマー
である。
アクリル系プレポリマーにはポリエステルアク
リレート型、エポキシアクリレート型、ウレタン
アクリレート型等があり、機能、用途に応じ、そ
れぞれプレポリマーが適宜使用されている。
中でもウレタンアクリレート型は特公昭48−
41708、特公昭55−8013等で指摘されているよう
に、他のプレポリマーに比べ空気硬化性がよく、
強靭な塗膜を形成し、鉄やガラスに対する密着性
に優れること、また一方ではイソシアネートの反
応性によつて種々の違つた構造を持つウレタンア
クリレートの開発が期待できる等の理由で、将来
的にも有望視されている。
Ｃ 発明が解決しようとする問題点
前述のように、ウレタンアクリレートを製造す
る際には、イソシアネートが反応性に富むためい
ろいろな分子設計が可能であり、多くの可能性を
秘めてはいるが、実際に市販されているウレタン
アクリレートの種類は少ない。この中で従来より
も更に優れた高度及び鉄面密着性を有するウレタ
ンアクリレートが現在望まれている。
Ｄ 問題点を解決するための手段
このような状況に鑑み、本発明者等は、鋭意検
討した結果、下記の一般式（）
〔式中、R1は−Ｈまたは−CH3
R2は炭素数１〜６の側鎖を有しまたは有しな
いアルキレン基、または
−（−CH2CH2−Ｏ−）n−CH2CH2−、
ｍ＝１〜５、
R3は
A. Industrial fields of application The compound of the present invention can be homopolymerized or copolymerized with appropriate reactive monomers using heat, ultraviolet rays, electron beams, etc., and can be used in paints, inks, adhesives, etc.
In addition to being used for yeast immobilization, dental filling materials, etc.
This invention relates to radically polymerizable urethane (meth)acrylates that utilize the property of being cured by ultraviolet light and are useful for printing plate materials, photoresists, resist inks for printed wiring, and the like. B. Prior Art Radically polymerizable urethane (meth)acrylate is often used as an ultraviolet curable prepolymer. Ultraviolet curable resin is a resin that changes from liquid to solid when exposed to ultraviolet rays.
It usually consists of a reactive prepolymer, a reactive diluent, and a photopolymerization initiator. The mainstream of these reactive prepolymers is acrylic prepolymers. Acrylic prepolymers include polyester acrylate types, epoxy acrylate types, urethane acrylate types, etc., and each prepolymer is used as appropriate depending on the function and application. Among them, the urethane acrylate type was specially developed in 1974.
As pointed out in 41708, Japanese Patent Publication No. 55-8013, etc., it has better air curing properties than other prepolymers.
In the future, urethane acrylate is expected to be developed because it forms a strong coating film and has excellent adhesion to iron and glass, and on the other hand, it can be expected to develop urethane acrylate with various different structures depending on the reactivity of isocyanate. is also seen as promising. C Problems to be Solved by the Invention As mentioned above, when producing urethane acrylate, various molecular designs are possible due to the high reactivity of isocyanate, and although it has many possibilities, There are actually only a few types of urethane acrylate on the market. Among these, there is currently a demand for urethane acrylates that have better adhesion and iron surface adhesion than conventional ones. D. Means for Solving the Problems In view of this situation, the inventors of the present invention, as a result of intensive study, developed the following general formula (). [In the formula, R 1 is -H or -CH 3 R 2 is an alkylene group with or without a side chain having 1 to 6 carbon atoms, or -(-CH 2 CH 2 -O-) n -CH 2 CH 2 −, m=1~5, R 3 is
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】−（−CH2−）6−、[Formula] −(−CH 2 −) 6 −,
【式】
からなる群から選ばれた置換基。
ｎは化合物の分子量が5000以上50000以下にな
るように５〜100の整数の中から選ばれた数。〕
で表わされるウレタン（メタ）アクリレートが、
硬度、鉄面に対する密着性及び屈曲性に優れた硬
化物を生成することを見出し、本発明を成すに至
つた。
なお、本発明者等は、先に本物質と同一構造を
もつが、分子量は異なる（分子量5000以下と限
定）オリゴマーを発明した（特願昭59−147133）。
しかしながら、本発明者等は更に該オリゴマーを
検討して行つた結果、該オリゴマーの分子量は
5000以上でもプレポリマーとしての機能を十分に
果し、しかもその分子量を上げることによつて、
硬度及び屈曲性の点で更に優れた性能を有するこ
とを見出し、本発明を成すに至つた。
本発明のウレタン（メタ）アクリレートは、例
えば一般式（）で表わされるジイソシアネート
と（）で表わされるスピログリコールとを
〔Ｏ＝Ｃ＝Ｎ−R3−Ｎ＝Ｃ＝Ｏ〕 ……（）
下記のように反応させて、一般式（）で表わ
される化合物Ａをつくり、
この化合物Ａに、下記の一般式（）で表わさ
れる（メタ）アクリレートを
（R1，R2は一般式（）における場合と同じ意
味をもつ）
下記のように反応させることにより製造され
る。
上記の一般式（）のジイソシアネートと
（）のスピログリコールとの反応は、ジブチル
スズラウレート等の金属化合物や３級アミン等の
触媒下で進行する。（メタ）アクリレートの重合
禁止剤の代表的なものとしては、ヒドロキノンモ
ノメチルエーテル（MEHQ）等がある。反応は、
無溶剤下で行なうか、必要とあれば、生成物と相
溶性のある溶媒下で行なうこともできる。
Ｅ 実施例
以下の実施例を示す。
実施例 １
温度計、冷却管、撹拌装置を備えた１の４つ
口フラスコに、２，４−トリレンジイソシアネー
ト（TDI）〔東京化成（株）製〕174g（1.0モル）
と、スピログリコール〔三菱瓦斯化学（株）製〕
273g（0.9モル）及びテトラヒドロフラン（THF）
500mlを加えた。次に、ジブチルスズジラウレー
ト0.2gを加え加熱した。反応開始と同時に発熱す
るが、反応時の最高温度は72℃であつた。発熱に
よる温度上昇が終つたのち、60℃で約２時間撹拌
を続けた。得られた反応物にヒドロキノンモノメ
チルエーテル（MEHQ）0.02g、２−ヒドロキシ
エチルアクリレート（HEA）21g（0.18モル）を
加えた。この際も反応時の最高温度は70℃であつ
た。発熱が終つた後、さらに60℃で約１時間撹拌
を続けた。得られた反応物は、エバポレーターで
THFを留去してから、40℃で３時間減圧乾燥
（５mmHg）させることにより、固体状の淡黄物質
を得た。
この淡黄色物質の特徴的なIRピークを以下に
示す。
3330cm-1 Ｎ−Ｈの伸縮振動による吸収
2960cm-1
2830cm-1脂肪族Ｃ−Ｈの伸縮振動
1720cm-1付近 ウレタン結合のＣ＝Ｏ及びアク
リロイル基のエステル結合
1610cm-1
1590cm-1ベンゼン核Ｃ＝Ｃ伸縮振動
イソシアネート基の吸収2270-1cmは全くみられ
なかつた。
実施例 ２
実施例１の２，４−トリレンジイソシアネート
を、イソホロンジイソシアネート（IPDI）に変
え、それ以外は、実施例１と同様に行なつた。そ
の結果、固体状の白色物質を得た。
Ｆ 発明の効果
実施例１，２で得られたウレタンアクリレート
を用い、表−１のような配合で光硬化性樹脂を得
た。A substituent selected from the group consisting of [Formula]. n is a number selected from integers from 5 to 100 such that the molecular weight of the compound is 5,000 or more and 50,000 or less. ] Urethane (meth)acrylate represented by
It was discovered that a cured product with excellent hardness, adhesion to iron surfaces, and flexibility can be produced, and the present invention was completed. The present inventors previously invented an oligomer that has the same structure as the present substance but has a different molecular weight (limited to a molecular weight of 5,000 or less) (Japanese Patent Application No. 147,133/1982).
However, as a result of further examination of the oligomer, the present inventors found that the molecular weight of the oligomer was
Even if it has a molecular weight of 5,000 or more, it still functions well as a prepolymer, and by increasing its molecular weight,
It was discovered that it has even better performance in terms of hardness and flexibility, and the present invention was completed. The urethane (meth)acrylate of the present invention is produced by combining, for example, a diisocyanate represented by the general formula () and a spiroglycol represented by () [O=C=N- R3 -N=C=O]...() Create a compound A represented by the general formula () by reacting as shown below, To this compound A, (meth)acrylate represented by the following general formula () is added. (R 1 and R 2 have the same meanings as in general formula ()) It is produced by reacting as shown below. The reaction between the diisocyanate of the general formula () and the spiroglycol of the general formula () proceeds under a catalyst such as a metal compound such as dibutyltin laurate or a tertiary amine. Typical polymerization inhibitors for (meth)acrylate include hydroquinone monomethyl ether (MEHQ). The reaction is
The reaction can be carried out without a solvent or, if necessary, in a solvent that is compatible with the product. E Examples The following examples are shown. Example 1 174 g (1.0 mol) of 2,4-tolylene diisocyanate (TDI) [manufactured by Tokyo Kasei Co., Ltd.] was placed in a four-neck flask equipped with a thermometer, a cooling tube, and a stirring device.
and spiroglycol [manufactured by Mitsubishi Gas Chemical Co., Ltd.]
273g (0.9mol) and tetrahydrofuran (THF)
Added 500ml. Next, 0.2 g of dibutyltin dilaurate was added and heated. Heat was generated at the same time as the reaction started, and the maximum temperature during the reaction was 72°C. After the temperature rise due to heat generation had ended, stirring was continued at 60°C for about 2 hours. 0.02 g of hydroquinone monomethyl ether (MEHQ) and 21 g (0.18 mol) of 2-hydroxyethyl acrylate (HEA) were added to the obtained reaction product. In this case as well, the maximum temperature during the reaction was 70°C. After the exotherm had ended, stirring was continued for about 1 hour at 60°C. The obtained reaction product is evaporated in an evaporator.
After THF was distilled off, a solid pale yellow substance was obtained by drying under reduced pressure (5 mmHg) at 40°C for 3 hours. The characteristic IR peak of this pale yellow substance is shown below. 3330cm -1 Absorption due to stretching vibration of N-H 2960cm -1 2830cm -1 Stretching vibration of aliphatic C-H Around 1720cm -1 C=O of urethane bond and ester bond of acryloyl group 1610cm -1 1590cm -1 Benzene nucleus C =C stretching vibration Absorption of isocyanate groups at 2270 -1 cm was not observed at all. Example 2 The same procedure as in Example 1 was carried out except that 2,4-tolylene diisocyanate in Example 1 was replaced with isophorone diisocyanate (IPDI). As a result, a solid white substance was obtained. F Effects of the Invention Using the urethane acrylates obtained in Examples 1 and 2, photocurable resins were obtained with the formulations shown in Table 1.
【表】
表−１の配合で得られた樹脂を鋼板上に塗布
し、120W／cm出力の高圧水銀灯10cm直下に10秒
間静止して露光させ塗膜を得た。得られた塗膜の
物性試験結果を表−２に示す。[Table] The resin obtained with the formulation shown in Table 1 was applied onto a steel plate, and exposed to light for 10 seconds directly under a high-pressure mercury lamp 10 cm with an output of 120 W/cm to obtain a coating film. Table 2 shows the physical property test results of the obtained coating film.
Claims (1)
いアルキレン基、または −（−CH2CH2−Ｏ−）n−CH2CH2−、 ｍ＝１〜５、 R3は 【式】【式】 【式】【式】 【式】 【式】 【式】 【式】 【式】 【式】【式】 【式】−（−CH2−）6−， 【式】 からなる群から選ばれた置換基。 ｎは化合物の分子量が5000以上50000以下にな
るように５〜100の整数の中から選ばれた数。〕 で表わされるウレタン（メタ）アクリレート。[Claims] 1. The following general formula [In the formula, R 1 is -H or -CH 3 R 2 is an alkylene group with or without a side chain having 1 to 6 carbon atoms, or -(-CH 2 CH 2 -O-) n -CH 2 CH 2 −, m=1~5, R 3 is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] - ( −CH 2 −) 6 −, a substituent selected from the group consisting of [Formula]. n is a number selected from integers from 5 to 100 such that the molecular weight of the compound is 5,000 or more and 50,000 or less. ] Urethane (meth)acrylate represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60164913A JPS6225115A (en) | 1985-07-25 | 1985-07-25 | Urethane acrylate or methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60164913A JPS6225115A (en) | 1985-07-25 | 1985-07-25 | Urethane acrylate or methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6225115A JPS6225115A (en) | 1987-02-03 |
| JPH032448B2 true JPH032448B2 (en) | 1991-01-16 |
Family
ID=15802236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60164913A Granted JPS6225115A (en) | 1985-07-25 | 1985-07-25 | Urethane acrylate or methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6225115A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107427414B (en) * | 2015-03-31 | 2021-07-02 | 三井化学株式会社 | Polymerizable monomer, composition, adhesive dental material and kit for dental materials |
-
1985
- 1985-07-25 JP JP60164913A patent/JPS6225115A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6225115A (en) | 1987-02-03 |
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