JPS6119604A - Production of water-soluble photopolymerization initiator - Google Patents
Production of water-soluble photopolymerization initiatorInfo
- Publication number
- JPS6119604A JPS6119604A JP14081884A JP14081884A JPS6119604A JP S6119604 A JPS6119604 A JP S6119604A JP 14081884 A JP14081884 A JP 14081884A JP 14081884 A JP14081884 A JP 14081884A JP S6119604 A JPS6119604 A JP S6119604A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- photopolymerization initiator
- water
- cyclodextrin
- examples
- 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.)
- Pending
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- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 ［発明の技術分野１ 本発明は水溶性光重合開始剤の製法に関する。[Detailed description of the invention] [Technical field of invention 1 The present invention relates to a method for producing a water-soluble photopolymerization initiator.
［従来技ｖ＃］
酵素電極は微量の有機成分を連、続的、かつ迅速に測定
する手段として急速に普及し始めている。[Prior art v#] Enzyme electrodes are rapidly becoming popular as a means for continuously and rapidly measuring trace amounts of organic components.
このような酵素電極は、酵素と光硬化性を有する水溶性
樹脂とを混合し、電気化学的トランスデユーサ−上に塗
布し、紫外線で硬化させて製造されている。Such enzyme electrodes are manufactured by mixing an enzyme and a photocurable water-soluble resin, coating the mixture on an electrochemical transducer, and curing it with ultraviolet light.
たとえば、酵素としてグルコースオキシグーゼを用い、
トランスデユーサ−として酸素電極を用いると、固定化
酵素膜内で式（１）：
で表わされる反応がおこる。式（１）で表される反応で
酸素が消費され、その１＃蝉量からグルコース濃度を知
ることができる。またｐＨ電極を用いて生成したグルコ
ン酸を測定してもよい。For example, using glucose oxyguse as the enzyme,
When an oxygen electrode is used as a transducer, a reaction expressed by formula (1) occurs within the immobilized enzyme membrane. Oxygen is consumed by the reaction represented by formula (1), and the glucose concentration can be determined from the amount of oxygen consumed. Alternatively, the generated gluconic acid may be measured using a pH electrode.
このような酵素電極の構成を第１図に示す１図中、（１
）は酸素電極またはｐＨ電極で、■は固定化酵素膜であ
る。The configuration of such an enzyme electrode is shown in FIG.
) is an oxygen electrode or a pH electrode, and ■ is an immobilized enzyme membrane.
酵素の固定化にはいろいろな方法があるが、その１つに
７オトレジストによる包接法がある。There are various methods for immobilizing enzymes, one of which is the inclusion method using 7-otoresist.
７オトレジストとしては、ポリエチレングリコ゛−ルの
両末端にアクリル基、メタクリル基などのビニル基を有
する水溶性の７オトレジスト（以下、多官能性（メタ）
アクリレート系モノマーという）が好ましく用いられて
いる。The 7-otoresist is a water-soluble 7-otoresist (hereinafter referred to as polyfunctional (meth)) having a vinyl group such as an acrylic group or a methacrylic group at both ends of polyethylene glycol.
acrylate monomers) are preferably used.
しかし、水溶性の光重合開始剤がほとんどなく、ベンゾ
インエチルエーテルなどを水中に分散させて使用してい
るのが実状であり、重合には再現性がな（、重合時間も
長いものである。However, there are almost no water-soluble photopolymerization initiators, and the reality is that benzoin ethyl ether or the like is used dispersed in water, and the polymerization is not reproducible (and the polymerization time is long).
［発明の概要］
本発明者らは上記のごと！＆実状に鑑み、水溶性光重合
開始剤をうるため鋭意検討を重ねた結果、本発明を完成
した。[Summary of the invention] The inventors have accomplished the above! & In view of the actual situation, the present invention was completed as a result of intensive studies to obtain a water-soluble photopolymerization initiator.
すなわち本発明は、光重合開始剤およびシクロデキスト
リンの両方を溶かす溶媒中に両者を溶解させ、そののち
溶媒を蒸発させることを特徴とする水溶性光重合開始剤
の製法に関する。That is, the present invention relates to a method for producing a water-soluble photopolymerization initiator, which is characterized by dissolving both the photopolymerization initiator and cyclodextrin in a solvent, and then evaporating the solvent.
本発明の製法によりえちれる光重合開始剤は、水溶性で
あるため再現性よく重合触媒として働き、かつおどろく
べきことに包接による重合開始能力の低下がなく、有機
溶媒中のベンゾインエチルエーテルなどと同程度の重合
開始速度を有するものである。Since the photopolymerization initiator produced by the production method of the present invention is water-soluble, it works as a polymerization catalyst with good reproducibility, and surprisingly, there is no decrease in polymerization initiation ability due to inclusion, and it is effective for benzoin ethyl ether in organic solvents. It has a polymerization initiation rate comparable to that of .
Ｅ発明の実施例］
本発明に用いるシクロデキストリンとしては、ａ−、β
−１γ−シクロデキストリンがあげられる。E Examples of the invention] Cyclodextrins used in the invention include a-, β
-1γ-cyclodextrin is mentioned.
本発明に用いる光重合開始剤としては、′ベンゾイン、
ベンゾインメチルエーテル、ベンゾイルエチルエーテル
、ベンゾフェノン、２．２’−アゾビスプロパンなどが
あげられるが、これらに限定されるものではなく、シク
ロデキストリンを溶解する溶媒に溶解°シ、そののち溶
媒を蒸発させることができるものであればよい。The photopolymerization initiators used in the present invention include 'benzoin,
Examples include, but are not limited to, benzoin methyl ether, benzoylethyl ether, benzophenone, 2,2'-azobispropane, etc. Dissolve in a solvent that dissolves cyclodextrin, and then evaporate the solvent. It is fine as long as it can be done.
本発明に用いる溶媒としては、シクロデキストリンおよ
び光重合開始剤の両者を溶かしたのち、該溶媒を蒸発さ
せることができるものであればとくに限定される□こと
なく使用しうる。このような溶媒の具体例としては、ジ
メチルスルホキシド、ジメチルホルムアミド、Ｎ−メチ
ルピロリドンなどヤ
があげられる。The solvent used in the present invention is not particularly limited and may be used as long as it can evaporate the solvent after dissolving both the cyclodextrin and the photopolymerization initiator. Specific examples of such solvents include dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, and the like.
前記光重合開始剤とシクロデキストリンとの使用割合は
、経済性、結合速度、固定化膜の機械的強度などの点か
ら光重合開始剤１モルに対しで１〜１０モルの範囲が好
ましく、１〜２モルであることがさらに好ましい。The ratio of the photopolymerization initiator and cyclodextrin used is preferably in the range of 1 to 10 moles per mole of the photopolymerization initiator from the viewpoint of economy, binding rate, mechanical strength of the immobilized film, etc. More preferably, the amount is 2 mol.
溶媒の使用量は、光重合開始剤およびシクロデキストリ
ンを溶解する量であればとくに限定はないが、こののち
行なう蒸発工程を短かくするという点から少ない方が好
ましい。The amount of solvent to be used is not particularly limited as long as it dissolves the photopolymerization initiator and cyclodextrin, but a smaller amount is preferable in order to shorten the subsequent evaporation step.
シクロデキストリンおよび光重合開始剤を溶媒に溶解さ
せる温度には、とくに制限はない。There is no particular restriction on the temperature at which the cyclodextrin and photopolymerization initiator are dissolved in the solvent.
つぎに包接化合物である水溶性光重合開始剤の製法を本
発明の一実施態様である具体例にもとづき説明する。Next, a method for producing a water-soluble photopolymerization initiator, which is an clathrate compound, will be explained based on a specific example that is an embodiment of the present invention.
まず、光重合開始剤およびシクロデキストリンの両方を
溶かす溶媒に両者を溶解させる。First, a photopolymerization initiator and a cyclodextrin are dissolved in a solvent that dissolves both.
えられた溶液から溶媒をロータリーエバポレーターなど
を用いて蒸発させ、残査を水に溶解させ、不溶物（沈澱
）を遠心分離、櫨過などの方法により除去することによ
り、水溶性光重合開始剤の水溶液がえられる。The solvent is evaporated from the resulting solution using a rotary evaporator, etc., the residue is dissolved in water, and the insoluble matter (precipitate) is removed by centrifugation, filtration, etc. to obtain a water-soluble photopolymerization initiator. An aqueous solution of
このようにしてえちれた本発明による光重合開始剤は、
一般に多官能性（メタ）アクリレート系モノマーの光重
合開始剤として好適に使用される。The photopolymerization initiator according to the present invention obtained in this way is
Generally, it is suitably used as a photopolymerization initiator for polyfunctional (meth)acrylate monomers.
前記多官能性（メタ）アクリレート系モノマーの具体例
としては、エチレングリコールジ（ツタ）アクリレート
、ジエチレングリコール（メタ）アクリレート、トリエ
チレングリコール（メタ）アクリレート、ＰＥに ＃
２００ノ（メタ）アクリレート、ＰＥＧ ＃ ４００ノ
（メタ）アクリレート、ＰＥＣ４６００ジ（メタ）アク
リレート、Ｆリメチロールプロパントリ（メタ）アクリ
レート、ジプロピレングリコール（メタ）アクリレート
、ＰＰＧ ＃ ４００ジ（メタ）アクリレ−）、ネオペ
ンチルグリコールジ（メタ）アクリレート、１．３−ブ
チレングリコールジ（メタ）７クリレート、ジプロモネ
オベンチルグリコールジ（メタ）アクリレ−Ｆなどがあ
げられるが、これらに限定されるものではない。Specific examples of the polyfunctional (meth)acrylate monomer include ethylene glycol di(vine) acrylate, diethylene glycol (meth)acrylate, triethylene glycol (meth)acrylate, and PE.
200 (meth)acrylate, PEG #400 (meth)acrylate, PEC4600 di(meth)acrylate, F-limethylolpropane tri(meth)acrylate, dipropylene glycol (meth)acrylate, PPG #400 di(meth)acrylate ), neopentyl glycol di(meth)acrylate, 1,3-butylene glycol di(meth)7 acrylate, dipromoneobentyl glycol di(meth)acrylate-F, etc., but are not limited to these. do not have.
以下、実施例に基づき本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail based on Examples.
実施例１
ペン・ジインエチルエーテル０．０１部（重量部、以下
同様）およびβ−シクロデキストリン１ｓを１００部の
ジメチルスルホキシドに溶解させたのち、口−タリーエ
バボレーターを用いてｔ＃媒を蒸発させた。ついで蒸留
水１００部を加えて残査を溶解させたのち、５０００に
で１０分間遠心分離して沈澱を除去した。Example 1 After dissolving 0.01 part of pen-diyne ethyl ether (parts by weight, same hereinafter) and 1s of β-cyclodextrin in 100 parts of dimethyl sulfoxide, the t# medium was evaporated using a mouth-talley evaporator. Ta. Next, 100 parts of distilled water was added to dissolve the residue, and the mixture was centrifuged at 5000 °C for 10 minutes to remove the precipitate.
えちれた水溶液１０部にＰＥ（、＠ Ｚｏｏジメタクリ
レート（商品名二ＮＫエステル９Ｇ、新中村化学＠１ｌ
）０．５部、グルコースオキシダーゼ０．１部を溶解さ
せ、酸素電極上に塗布した。そののち塗布物に１５０＋
Ｗ／ｃｍ２の超高圧水銀灯光を１分間照射したところ、
塗布物は寒天状に硬化し、酵素は水中に溶は出すことな
く酸素電極上に固定された。Add PE (@Zoo dimethacrylate (trade name: 2NK Ester 9G, Shin Nakamura Chemical @1l) to 10 parts of the aqueous solution.
) and 0.1 part of glucose oxidase were dissolved and applied on the oxygen electrode. After that, apply 150+
When irradiated with ultra-high pressure mercury lamp light of W/cm2 for 1 minute,
The coating hardened into agar-like form, and the enzyme was immobilized on the oxygen electrode without being dissolved in water.
えちれた酵素電極と酸素電極とを検体試料に入れ両者の
電圧の差を測定したところ、グルコース濃度を測定する
ことがで鯵だ。By inserting a well-engineered enzyme electrode and an oxygen electrode into a specimen sample and measuring the difference in voltage between the two, it was possible to measure the glucose concentration.
実施例２
ベンゾフェノン０．０２部お上りα−シクロデキストリ
ン１部を１００部のトメチルピロリドンに溶解したのち
、ロータリーエバポレーターを用いて溶媒を蒸発させた
。ついで蒸留水１００部を加えて残査を溶解させたのち
、５０００Ｇで１０分間遠心分散して沈澱を除去した。Example 2 After dissolving 0.02 parts of benzophenone and 1 part of α-cyclodextrin in 100 parts of tomethylpyrrolidone, the solvent was evaporated using a rotary evaporator. Next, 100 parts of distilled water was added to dissolve the residue, and the mixture was centrifuged at 5000G for 10 minutes to remove the precipitate.
えられた水溶液１０部にＰＥに ＄ ６００ジメタクリ
レート（商品名：ＮＫエステル１４Ｇ１新中村化学特製
）０．６部、グルコースオキングーゼ０．２部を溶解さ
せ、ｌ５ＦＥＴ素子に塗布した。そののち塗布物に１５
０論−７Ｃ論２の超高圧水銀灯光を１分間照射したとこ
ろ、塗布物は寒天状に硬化し、酵素は水中に溶は出す
−ことなく、ｌ５ＦＥＴ素子上に固定された。In 10 parts of the resulting aqueous solution, PE, 0.6 part of $600 dimethacrylate (trade name: NK Ester 14G1 Shin-Nakamura Chemical Co., Ltd.) and 0.2 part of glucose okingase were dissolved and applied to the 15FET element. Then apply 15% to the applied product.
When irradiated with ultra-high pressure mercury lamp light from Theory 0-7C Theory 2 for 1 minute, the applied material hardened into an agar-like state, and the enzyme dissolved into water.
- fixed on the 15FET device without any problem.
えられた酵素固定ｌ５ＦＥＴ素子とｌ５ＦＥＴ素子とを
同時に標準検体試料に入れ、両者の電圧差を測定したと
ころ、グルコース濃度を測定することかで鯵な。When the obtained enzyme-immobilized 15FET element and the 15FET element were placed in a standard sample at the same time and the voltage difference between the two was measured, it was found that the glucose concentration was measured.
［発明の効果］
本発明の製法によると、光重合開始剤およびシクロデキ
ストリンを溶解する溶媒中に両者を溶解し、そののち溶
媒を除去することにより、良好な光重合開始性を有する
水溶性光重合開始剤を簡単にうろことができる。[Effects of the Invention] According to the production method of the present invention, a water-soluble photopolymerization initiator and a cyclodextrin having good photopolymerization initiating properties are produced by dissolving the photopolymerization initiator and cyclodextrin in a solvent and then removing the solvent. Polymerization initiator can be easily removed.
第１図は酵素電極の概念を示す説明図である。
（図面の符号）
（１）：酸素電極またはｐｔｔ電極
電極面定化酵素膜
代理人 大 岩 増 雄 （ほか２名）２１図
手続補正書（自発）
昭和 年 月 日
１、事件の表示 特願昭５９−１４０８１６号２、
発明の名称
水溶性光重合開始剤の製法
３、補正をする者
代表者片由仁へ部
４、代理人
５、補正の対象
（１）明細書の「発明の詳細な説明」の欄６、補正の内
容
（ｘ）明細書４頁ｓ〜６行の「ベンゾイルエチルエーテ
ル」ヲ「ベンゾインエチルエーテル」ト補正する。
以 上
や
＝２６FIG. 1 is an explanatory diagram showing the concept of an enzyme electrode. (Drawing code) (1): Oxygen electrode or PTT electrode electrode surface fixed enzyme membrane agent Masuo Oiwa (and 2 others) Amendment to Figure 21 procedure (voluntary) Showa year, month, day 1, case indication Patent application 1983-140816 No. 2,
Name of the invention Process for producing a water-soluble photopolymerization initiator 3, Person making the amendment Representative Katayuni Department 4, Agent 5, Subject of amendment (1) Column 6 of "Detailed description of the invention" in the specification, Amendment Contents (x) "Benzoyl ethyl ether" on page 4, lines s to 6 of the specification shall be amended to "benzoin ethyl ether". That's it = 26
Claims (3)
溶かす溶媒中に両者を溶解させ、そののち溶媒を蒸発さ
せることを特徴とする水溶性光重合開始剤の製法。(1) A method for producing a water-soluble photopolymerization initiator, which comprises dissolving both the photopolymerization initiator and cyclodextrin in a solvent, and then evaporating the solvent.
特許請求の範囲第（１）項記載の製法。(2) The method according to claim (1), wherein the photopolymerization initiator is benzoin ethyl ether.
す溶媒がジメチルスルホキシドである特許請求の範囲第
（１）項または第（２）項記載の製法。(3) The manufacturing method according to claim (1) or (2), wherein the solvent for dissolving both the photopolymerization initiator and cyclodextrin is dimethyl sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14081884A JPS6119604A (en) | 1984-07-05 | 1984-07-05 | Production of water-soluble photopolymerization initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14081884A JPS6119604A (en) | 1984-07-05 | 1984-07-05 | Production of water-soluble photopolymerization initiator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6119604A true JPS6119604A (en) | 1986-01-28 |
Family
ID=15277435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14081884A Pending JPS6119604A (en) | 1984-07-05 | 1984-07-05 | Production of water-soluble photopolymerization initiator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119604A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121210A (en) * | 1971-08-24 | 1983-07-19 | バイエル・アクチエンゲゼルシヤフト | Manufacture of instantaneous mouth discharging sublingual soft capsule medicine |
-
1984
- 1984-07-05 JP JP14081884A patent/JPS6119604A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121210A (en) * | 1971-08-24 | 1983-07-19 | バイエル・アクチエンゲゼルシヤフト | Manufacture of instantaneous mouth discharging sublingual soft capsule medicine |
| JPS6119604B2 (en) * | 1971-08-24 | 1986-05-17 | Bayer Ag |
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