JP2017023902A - Photo repair agent and application - Google Patents
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- 238000006471 dimerization reaction Methods 0.000 claims abstract description 39
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Abstract
Description
本発明は、光の照射を受けて互いに二量化する二量化基が導入された重合体を含む光修復剤に関する。 The present invention relates to a photorestoring agent comprising a polymer into which dimerization groups that dimerize with each other upon introduction of light are introduced.
膜分離技術は、汚染した水の浄化や混合溶液からの目的物質の回収・濃縮など幅広く利用されている。従来の分離膜では、長時間の使用により膜表面への汚染物質やタンパク質等が吸着 （ファウリング）し、分離膜が有する細孔が目詰まりするために分離性能が低下するといった問題がある。 Membrane separation technology is widely used for purification of contaminated water and recovery / concentration of target substances from mixed solutions. In conventional separation membranes, there is a problem in that the separation performance deteriorates because contaminants, proteins, and the like adsorb (fouling) on the membrane surface due to long-term use and the pores of the separation membrane are clogged.
ファウリングが生じた膜の分離性能を回復させるためには、膜表面の洗浄あるいは膜の交換が必要となり、これらの作業には多大なコストと労力が費やされる。そのため、現在、分離膜の長寿命化をはかるために、ファウリング物質の吸着を抑制する性質 （アンチファウリング性）を膜表面に付与する研究が精力的に行われている（参照：特許文献１）。
これまでに、膜表面への高アンチファウリング性ポリマーの修飾やコーティング材料を用いることによりアンチファウリング性を付与させることが試みられている。このような分離膜の分離性能の低下を抑制する技術の開発は、膜の洗浄や交換の頻度を軽減させることができ、企業や家庭において大きな経済効果をもたらすことが期待できる。しかし、従来の方法では完全にファウリングを抑制することは困難であり、より容易に膜性能を回復する技術や材料の開発が望まれている。
In order to recover the separation performance of the membrane in which fouling has occurred, it is necessary to clean the membrane surface or replace the membrane, and these operations are costly and labor intensive. For this reason, in order to extend the life of the separation membrane, research has been actively conducted to give the membrane surface the property of suppressing the adsorption of fouling substances (anti-fouling property) (see: Patent Literature). 1).
Until now, attempts have been made to impart antifouling properties by modifying a highly antifouling polymer on the film surface or using a coating material. The development of the technology that suppresses the decrease in the separation performance of the separation membrane can reduce the frequency of cleaning and replacement of the membrane, and can be expected to bring about a great economic effect in companies and homes. However, it is difficult to completely suppress fouling by the conventional method, and development of technology and materials that can more easily recover the film performance is desired.
従来の分離膜は、長時間の使用によりタンパク質や汚染物質などのファウリング物質が吸着し、膜の細孔が目詰まりすることから分離機能が著しく低下する。ファウリングが生じた分離膜の機能を回復させるためには、膜表面に吸着したファウリング物質の洗浄や新たな膜の交換を行う必要があり、洗浄や交換の頻度が高くなれば、環境負荷や経済的損失が大きくなる。近年、排除体積の大きなポリマーや両性イオンを有するポリマーで材料表面を修飾やコーティングすることにより、ファウリングの抑制が試みられている。
しかし、形成したポリマー層は長時間の使用により劣化や損傷が生じ、その部位からファウリング物質の吸着が誘発され、長期間のアンチファウリング性の保持は未だに実現していない。 表面修飾による分離膜の長寿命化は、さらに高アンチファウリング性を有する化学物質・修飾方法の開発が必要であり、その物質が高価で修飾方法が複雑になれば、広範に応用されている分離膜分野への普及が困難となる。
Conventional separation membranes, when used for a long time, adsorb fouling substances such as proteins and contaminants and clog the pores of the membrane, so that the separation function is significantly reduced. In order to restore the function of the separation membrane in which fouling has occurred, it is necessary to clean the fouling substance adsorbed on the membrane surface or replace a new membrane. And economic loss increases. In recent years, attempts have been made to suppress fouling by modifying or coating the surface of a material with a polymer having a large excluded volume or a polymer having zwitterions.
However, the formed polymer layer is deteriorated or damaged by long-term use, and the adsorption of the fouling substance is induced from the site, and the long-term antifouling property has not been realized yet. Extending the life of separation membranes by surface modification requires the development of chemical substances and modification methods with even higher anti-fouling properties, and they are widely applied if the substances are expensive and the modification methods become complicated. Dissemination to the separation membrane field becomes difficult.
これまでに、様々な方法によって材料表面にアンチファウリング性を付与する報告がなされている。例えば、以下のように報告がある。 So far, various methods have been reported to impart anti-fouling properties to the material surface. For example, there are reports as follows.
生体細胞膜を構成するリン脂質の構造を模倣して合成された２−メタクリロイルオキシエチルホスホリルコリンからなるポリマーをシリコン基板表面上に修飾することによりタンパク質の非特異的吸着を抑制できることが報告されている ｛参照非特許文献１： Ishihara, K., Inoue, Y. Advances in Science and Technology.,76, 1 -9 (2010)｝。
非特許文献１に記載の方法では、材料表面への非特異的吸着の抑制を可能にしているが、長期使用中にファウリングが生じた際にファウリング物質の除去はできない。 加えて、本発明の光修復剤に含まれている重合体の構成は、非特許文献１に記載の重合体の構成と比較して、明らかに異なる。
It has been reported that non-specific adsorption of proteins can be suppressed by modifying a polymer composed of 2-methacryloyloxyethyl phosphorylcholine, which is synthesized by mimicking the structure of phospholipids constituting a biological cell membrane, on the surface of a silicon substrate. { Reference Non-Patent Document 1: Ishihara, K., Inoue, Y. Advances in Science and Technology., 76, 1-9 (2010)}.
The method described in Non-Patent Document 1 makes it possible to suppress nonspecific adsorption on the material surface, but cannot remove the fouling substance when fouling occurs during long-term use. In addition, the structure of the polymer contained in the photorestoring agent of the present invention is clearly different from the structure of the polymer described in Non-Patent Document 1.
また、クマリンの可逆的な光二量化反応を利用して、可逆的に物性を変化させる材料が報告されている。 例えば、ポリマー鎖中にクマリンを導入し光照射することにより、クマリンの結合・解離によりゲルからゾル、ゾルからゲルへと状態変化（ゾル-ゲル相転移）するポリマー系が報告されている｛参照非特許文献２：Ajiro, H., Akashi, M. Chem. Lett.,43,1613-1615 (2014)｝。
非特許文献２に記載の方法では、膜表面にコーティングする技術ではなく、またアンチファウリング性を有した物質でない。
In addition, a material that reversibly changes physical properties using a reversible photodimerization reaction of coumarin has been reported. For example, a polymer system that changes state from gel to sol and sol to gel (sol-gel phase transition) by coumarin binding / dissociation by introducing coumarin into the polymer chain and irradiating with light has been reported {see Non-Patent Document 2: Ajiro, H., Akashi, M. Chem. Lett., 43, 1613-1615 (2014)}.
The method described in Non-Patent Document 2 is not a technique for coating the film surface, and is not a substance having antifouling properties.
特許文献１は、「２−メタクリロイルオキシエチルホスホリルコリン及びカチオン性（メタ）アクリル酸エステルを含む単量体組成物を重合して得た共重合体と、水とを含むポリアミド逆浸透膜用の表面処理剤」を開示している。
しかし、本発明の光修復剤に含まれている重合体の構成は、特許文献１に記載の重合体の構成とは比較して、明らかに異なる。
Patent Document 1 states that “a surface for a polyamide reverse osmosis membrane comprising a copolymer obtained by polymerizing a monomer composition containing 2-methacryloyloxyethyl phosphorylcholine and a cationic (meth) acrylic ester, and water. "Treatment agent" is disclosed.
However, the structure of the polymer contained in the photorestoring agent of the present invention is clearly different from the structure of the polymer described in Patent Document 1.
従来、分離膜表面へのファウリングを抑制する方法は、アンチファウリング性を有するポリマーの修飾やコーティングが主流であった。 しかし、膜表面に形成されたポリマー層の劣化や損傷によりアンチファウリング性が低下することが問題となっている。
これにより、ファウリングが生じた際に外部刺激により簡便に分離機能が回復するような新たなコーティング剤が求められている。
Conventionally, the method of suppressing fouling on the surface of the separation membrane has been mainly modified or coated with a polymer having anti-fouling properties. However, there is a problem that the anti-fouling property is lowered due to deterioration or damage of the polymer layer formed on the film surface.
Accordingly, there is a demand for a new coating agent that can easily recover the separation function by external stimulation when fouling occurs.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、光の照射を受けて互いに二量化する二量化基が下記式（１）に導入された単量体を重合して得られた重合体、より詳しくは、光の照射を受けて互いに二量化する二量化基を含む単量体と下記式（１）で表される単量体を重合して得た共重体を、光修復剤として用いることで、上記の課題を解決することの知見を見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors polymerized monomers in which dimerization groups that dimerize with each other upon irradiation with light were introduced into the following formula (1). More specifically, an obtained polymer, more specifically, a copolymer obtained by polymerizing a monomer containing a dimerization group that dimerizes with each other upon irradiation with light and a monomer represented by the following formula (1): The present inventors have found the knowledge of solving the above problems by using it as a photorestoring agent, and have completed the present invention.
上記式（１）中、R1は水素原子又はメチル基を示し、R2及びR3は、それぞれ独立に、炭素数１〜４のアルキレン基を示し、R4、R5及びR6は、それぞれ独立に、炭素数１〜４のアルキル基を示す。 In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents an alkylene group having 1 to 4 carbon atoms, R 4, R 5 and R 6, Each independently represents an alkyl group having 1 to 4 carbon atoms.
すなわち、本発明は次の＜１＞〜＜７＞である。
＜１＞
光の照射を受けて互いに二量化する二量化基が下記式（１）に導入された単量体を重合して得られた重合体を含む光修復剤。
＜２＞
前記重合体は、光の照射を受けて互いに二量化する二量化基を含む単量体と前記式（１）で表される単量体を共重合して得た共重合体である＜１＞の光修復剤。
＜３＞
前記二量化基が、クマリン基、シンナモイル基、チミン基、ウラシル基およびアントラセン基からなる群から選ばれる少なくとも１種類の置換基である＜１＞又は＜２＞に記載の光修復剤。
＜４＞
前記二量化基を含む単量体が７-(２-メタクリロイルオキシクマリン)であり、かつ前記式（１）で表される単量体が２−メタクリロイルオキシエチルホスホリルコリンである＜１＞〜＜３＞のいずれか１に記載の光修復剤。
＜５＞
前記二量化基の構成単位と前記式（１）で表される単量体の構成単位のモル比が、２０〜９０：８０〜１０である＜１＞〜＜４＞のいずれか１に記載の光修復剤。
＜６＞
前記光修復剤は、以下のいずれか１の用途である＜１＞〜＜５＞のいずれか１に記載の光修復剤。
（１）表面処理剤
（２）生体材料保護剤
（３）接着剤
＜７＞
＜１＞〜＜６＞のいずれか１に記載の光修復剤が塗布された表面を有する材料。
That is, the present invention includes the following <1> to <7>.
<1>
A photorestoring agent comprising a polymer obtained by polymerizing a monomer in which dimerization groups that dimerize upon irradiation with light are introduced into the following formula (1).
<2>
The polymer is a copolymer obtained by copolymerizing a monomer containing a dimerization group which dimerizes with each other upon irradiation with light and a monomer represented by the formula (1) <1. > Light restoration agent.
<3>
The photorestoration agent according to <1> or <2>, wherein the dimerization group is at least one substituent selected from the group consisting of a coumarin group, a cinnamoyl group, a thymine group, a uracil group, and an anthracene group.
<4>
<1> to <3, wherein the monomer containing the dimerization group is 7- (2-methacryloyloxycoumarin) and the monomer represented by the formula (1) is 2-methacryloyloxyethyl phosphorylcholine. > The photorestoration agent of any one of>.
<5>
The molar ratio of the structural unit of the dimerization group and the structural unit of the monomer represented by the formula (1) is 20 to 90:80 to 10, and any one of <1> to <4>. Light repair agent.
<6>
The photorestoring agent according to any one of <1> to <5>, which is any one of the following uses.
(1) Surface treatment agent (2) Biomaterial protective agent (3) Adhesive <7>
<1>-<6> The material which has the surface in which the photorestoration agent of any one of <6> was apply | coated.
本発明の光修復剤は、表面に吸着したタンパク質等のファウリング物質を光照射により除去できる特性を有する。 The photorestoring agent of the present invention has a characteristic that fouling substances such as proteins adsorbed on the surface can be removed by light irradiation.
（光修復剤）
本発明の光修復剤は、光の照射を受けて互いに二量化する二量化基が下記式（１）に導入された単量体を重合して得られた重合体を含む。
より詳しくは、本発明の光修復剤は、光の照射を受けて互いに二量化する二量化基を含む単量体と下記式（１）で表される単量体を重合して得た共重体を含む。
(Light restoration agent)
The photorestoring agent of the present invention includes a polymer obtained by polymerizing monomers in which dimerization groups that dimerize with each other upon introduction of light are introduced into the following formula (1).
More specifically, the photorestoring agent of the present invention is a copolymer obtained by polymerizing a monomer containing a dimerization group that dimerizes with each other upon irradiation with light and a monomer represented by the following formula (1). Includes heavy body.
上記式（１）中、R1は水素原子又はメチル基を示し、R2及びR3は、それぞれ独立に、炭素数１〜４のアルキレン基を示し、R4、R5及びR6は、それぞれ独立に、炭素数１〜４のアルキル基を示す。 In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents an alkylene group having 1 to 4 carbon atoms, R 4, R 5 and R 6, Each independently represents an alkyl group having 1 to 4 carbon atoms.
｛式（１）で表される単量体｝
式（１）で表される単量体としては、例えば、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリメチルアンモニオ）エチルホスフェート、３−（（メタ）アクリロイルオキシ）プロピル−２'−（トリメチルアンモニオ）エチルホスフェート、４−（（メタ）アクリロイルオキシ）ブチル−２'−（トリメチルアンモニオ）エチルホスフェート、５−（（メタ）アクリロイルオキシ）ペンチル−２'−（トリメチルアンモニオ）エチルホスフェート、６−（（メタ）アクリロイルオキシ）ヘキシル−２'−（トリメチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリエチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリプロピルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリブチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリシクロヘキシルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）エチル−２'−（トリフェニルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）プロピル−２'−（トリメチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）ブチル−２'−（トリメチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）ペンチル−２'−（トリメチルアンモニオ）エチルホスフェート、２−（（メタ）アクリロイルオキシ）ヘキシル−２'−（トリメチルアンモニオ）エチルホスフェート等が挙げられる。
式（１）で表される単量体としては、中でも２−（（メタ）アクリロイルオキシ）エチル−２'−（トリメチルアンモニオ）エチルホスフェートが好ましく、さらに２−（メタクリロイルオキシ）エチル−２'−（トリメチルアンモニオ）エチルホスフェート｛２−メタクリロイルオキシエチルホスホリルコリンともいう。以下、「ＭＰＣ」と称する場合がある｝が入手性の点からは好ましい。
{Monomer represented by Formula (1)}
Examples of the monomer represented by the formula (1) include 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate, 3-((meth) acryloyloxy) propyl-2. '-(Trimethylammonio) ethyl phosphate, 4-((meth) acryloyloxy) butyl-2'-(trimethylammonio) ethyl phosphate, 5-((meth) acryloyloxy) pentyl-2 '-(trimethylammonio ) Ethyl phosphate, 6-((meth) acryloyloxy) hexyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 ′-(triethylammonio) ethyl phosphate, 2- ((Meth) acryloyloxy) ethyl-2 '-(tripropylammonio) Tyl phosphate, 2-((meth) acryloyloxy) ethyl-2 ′-(tributylammonio) ethyl phosphate, 2-((meth) acryloyloxy) ethyl-2 ′-(tricyclohexylammonio) ethyl phosphate, 2- ((Meth) acryloyloxy) ethyl-2 ′-(triphenylammonio) ethyl phosphate, 2-((meth) acryloyloxy) propyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyl Oxy) butyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) pentyl-2 ′-(trimethylammonio) ethyl phosphate, 2-((meth) acryloyloxy) hexyl-2 ′ -(Trimethylammonio) ethyl phosphate Etc.
As the monomer represented by the formula (1), 2-((meth) acryloyloxy) ethyl-2 ′-(trimethylammonio) ethyl phosphate is preferable, and 2- (methacryloyloxy) ethyl-2 ′ is more preferable. -(Trimethylammonio) ethyl phosphate {also called 2-methacryloyloxyethyl phosphorylcholine. Hereinafter, it may be referred to as “MPC”} is preferable from the viewpoint of availability.
（光の照射を受けて互いに二量化する二量化基）
本発明の「光の照射を受けて互いに二量化する二量化基」は、特定の波長光により分子を基底状態から励起状態にし、その励起状態の分子が二量体を形成すれば特に限定されないが、可逆的な光二量化反応を示すことが好ましい。
例えば、クマリン基、シンナモイル基、チミン基、ウラシル基およびアントラセン基等を例示できるが、クマリン基が好ましい。
(Dimerization groups that dimerize with each other when exposed to light)
The “dimerization group that dimerizes with each other upon irradiation with light” of the present invention is not particularly limited as long as the molecule is excited from the ground state by a specific wavelength light and the molecule in the excited state forms a dimer. However, it is preferable to show a reversible photodimerization reaction.
For example, a coumarin group, a cinnamoyl group, a thymine group, a uracil group, an anthracene group, etc. can be illustrated, but a coumarin group is preferable.
クマリンは、可逆的な光二量化反応を示すことが知られており、可視光を照射すると二量体を形成するが、二量化したクマリンに紫外光を照射すると単量体に開裂する。そこで、式（１）で表される単量体にクマリン（基）を導入することにより、光照射によってクマリンが結合・開裂してポリマー中の架橋密度が変化し、水への溶解性を制御できる。
すなわち、光の照射を受けて互いに二量化する二量化基としてクマリン基が導入された重合体では、３００〜４００nmの可視光を照射すれば、クマリンが二量体を形成し、３００nm以下の紫外光を照射すれば、クマリンが単量体を形成する。
Coumarin is known to exhibit a reversible photodimerization reaction, and forms a dimer when irradiated with visible light, but is cleaved into monomers when irradiated with ultraviolet light. Therefore, by introducing coumarin (group) into the monomer represented by formula (1), coumarin is bonded and cleaved by light irradiation, and the crosslink density in the polymer changes, thereby controlling the solubility in water. it can.
That is, in a polymer in which a coumarin group is introduced as a dimerization group that dimerizes with each other when irradiated with light, the coumarin forms a dimer when irradiated with visible light of 300 to 400 nm, and an ultraviolet of 300 nm or less. When irradiated with light, coumarin forms a monomer.
光の照射を受けて互いに二量化する二量化基としてシンナモイル基が導入された重合体では、３００〜４００nmを照射すれば、シンナモイルが二量体を形成し、３００nm以下を照射すれば、シンナモイルが単量体を形成する。
光の照射を受けて互いに二量化する二量化基としてチミン基が導入された重合体では、２７０〜３２０nmを照射すれば、チミンが二量体を形成し、２７０nm以下を照射すれば、チミンが単量体を形成する。
光の照射を受けて互いに二量化する二量化基としてウラシル基が導入された重合体では、２７０〜３２０nmを照射すれば、ウラシルが二量体を形成し、２７０nm以下を照射すれば、ウラシルが単量体を形成する。
光の照射を受けて互いに二量化する二量化基としてアントラセン基が導入された重合体では、３００〜４００nmを照射すれば、アントラセンが二量体を形成し、熱および３００nm以下を照射すれば、ウラシルが単量体を形成する
In a polymer in which cinnamoyl groups are introduced as dimerization groups that dimerize when irradiated with light, cinnamoyl forms a dimer when irradiated with 300 to 400 nm, and cinnamoyl is formed when irradiated with 300 nm or less. Form a monomer.
In a polymer in which a thymine group is introduced as a dimerization group that dimerizes upon irradiation with light, if 270 to 320 nm is irradiated, thymine forms a dimer, and if 270 nm or less is irradiated, thymine is Form a monomer.
In a polymer in which a uracil group is introduced as a dimerization group that dimerizes when irradiated with light, uracil forms a dimer when irradiated with 270 to 320 nm, and uracil is converted when irradiated with 270 nm or less. Form a monomer.
In a polymer in which anthracene groups are introduced as dimerization groups that dimerize with each other when irradiated with light, if anthracene forms a dimer when irradiated with 300 to 400 nm, and heat and 300 nm or less are irradiated, Uracil forms monomer
（光の照射を受けて互いに二量化する二量化基が式（１）に導入された単量体）
光の照射を受けて互いに二量化する二量化基が式（１）に導入された単量体の好ましい例としては、クマリン基が２−メタクリロイルオキシエチルホスホリルコリンに導入された単量体である。
(Monomer in which a dimerization group that dimerizes with each other by being irradiated with light is introduced into the formula (1))
A preferred example of the monomer in which a dimerization group that dimerizes upon irradiation with light is introduced into the formula (1) is a monomer in which a coumarin group is introduced into 2-methacryloyloxyethyl phosphorylcholine.
（光の照射を受けて互いに二量化する二量化基を含む単量体）
本発明の「光の照射を受けて互いに二量化する二量化基を含む単量体」の「単量体」は、光の照射を受けて互いに二量化する二量化基を含むことができる構造（特に、高分子構造）であれば特に限定されない。
例えば、トリエチルアミン、トリメチルアミン、塩化メタクリロイル、ポリエチルアミン、ポリビニルアミン、ポリエチレン、ポリプロピレン、ポリブテン、ポリ塩化ビニル、ポリエステル（ＰＥＴ）、ポリアミド、ポリカーボネートなどが挙げられる。この他に、アクリル酸系ポリマーを採用することもでき、（メタ）アクリル酸；アルキル（メタ）アクリレート；マレイン酸；ビニルスルホン酸；ビニルベンゼンスルホン酸；（メタ）アクリルアミド；アクリルアミドアルキルスルホン酸；（メタ）アクリロニトリル；ジメチルアミノプロピル（メタ）アクリルアミド等のアミノ置換（メタ）アクリルアミド；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等の（メタ）アクリル酸アミノ置換アルキルエステル；２−ヒドロキシエチル（メタ）アクリレート等のヒドロキシエチルメタクリレート；スチレン；ビニルピリジン；ビニルカルバゾール；ジメチルアミノスチレン；Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ'−ジメチル（メタ）アクリルアミド等のアルキル置換（メタ）アクリルアミド；酢酸ビニル；アリルアミン等を単独または２種以上組み合わせて使用することができる。
なお、本明細書において、「アクリル」または「メタクリル」を意味する場合には、「（メタ）アクリル」と表記する場合がある。
(Monomers containing dimerization groups that dimerize when irradiated with light)
The “monomer” of the “monomer containing a dimerization group that dimerizes with each other upon irradiation with light” of the present invention can include a dimerization group that dimerizes with each other upon irradiation with light. There is no particular limitation as long as it is (particularly a polymer structure).
Examples include triethylamine, trimethylamine, methacryloyl chloride, polyethylamine, polyvinylamine, polyethylene, polypropylene, polybutene, polyvinyl chloride, polyester (PET), polyamide, polycarbonate, and the like. In addition to this, an acrylic acid-based polymer can also be employed, (meth) acrylic acid; alkyl (meth) acrylate; maleic acid; vinyl sulfonic acid; vinyl benzene sulfonic acid; (meth) acrylamide; (Meth) acrylonitrile; amino substituted (meth) acrylamide such as dimethylaminopropyl (meth) acrylamide; amino (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Substituted alkyl ester; hydroxyethyl methacrylate such as 2-hydroxyethyl (meth) acrylate; styrene; vinyl pyridine; vinyl carbazole; dimethylaminostyrene; May be used alone or in combination of two or more allylamine;) acrylamide, N, N'-dimethyl (meth) alkyl-substituted acrylamide, (meth) acrylamide; vinyl acetate.
In the present specification, “acryl” or “methacryl” may be referred to as “(meth) acryl”.
（重合体）
本発明の「重合体（又は共重合体）」は、二量化基の構成単位と前記式（１）で表される単量体の構成単位のモル比が、２０〜９０：８０〜１０であり、好ましくは３５〜６５：６５〜３５であり、より好ましくは４０〜５０：６０〜５０である。
二量化基の構成単位が２０モル％以下であると二量体形成後においても水に可溶となり、９０モル％以上であると二量体が解離しても水に不溶となる。
(Polymer)
In the “polymer (or copolymer)” of the present invention, the molar ratio of the structural unit of the dimerization group and the structural unit of the monomer represented by the formula (1) is 20 to 90:80 to 10. Yes, preferably 35-65: 65-35, more preferably 40-50: 60-50.
When the structural unit of the dimerization group is 20 mol% or less, it becomes soluble in water even after dimer formation, and when it is 90 mol% or more, it becomes insoluble in water even when the dimer is dissociated.
本発明の重合体（又は共重合体）の分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により、標準ポリエチレングリコールを用いて換算した重量平均分子量で、好ましくは１,０００〜１,０００,０００、好ましくは１,０００〜５００,０００であり、特に好ましくは１０,０００〜１００,０００である。 The molecular weight of the polymer (or copolymer) of the present invention is a weight average molecular weight converted using standard polyethylene glycol by gel permeation chromatography (GPC), preferably 1,000 to 1,000,000, Preferably it is 1,000-500,000, Most preferably, it is 10,000-100,000.
本発明の好ましい重合体は、以下の式（２）で表される。式（２）中のｍ及びｎは、それぞれ、２０〜９０及び１０〜８０の整数である。 A preferred polymer of the present invention is represented by the following formula (2). M and n in Formula (2) are integers of 20 to 90 and 10 to 80, respectively.
本発明の重合体（又は共重合体）は、可逆的な光二量化反応に悪影響を与えるものでなければ、さらに他の単量体を組み合わせてもよい。 The polymer (or copolymer) of the present invention may be further combined with other monomers as long as it does not adversely affect the reversible photodimerization reaction.
（重合体の製造方法）
本発明の重合体（又は共重合体）は、自体公知の高分子の製造方法を採用することができるが、例えば以下を例示することができる。
(Method for producing polymer)
For the polymer (or copolymer) of the present invention, a method for producing a polymer known per se can be adopted. For example, the following can be exemplified.
光の照射を受けて互いに二量化する二量化基を式（１）に導入して、二量化基を含む式（１）の単量体を重合する、又は、二量化基を含む式（１）のオリゴマーを重合する。
または、式（１）の単量体を重合して重合体を得た後に、二量化する二量化基を該重合体に導入しても良い。
Dimerization groups that dimerize with each other upon introduction of light are introduced into formula (1) to polymerize the monomer of formula (1) containing a dimerization group, or formula (1 containing a dimerization group) ).
Or after polymerizing the monomer of Formula (1) and obtaining a polymer, you may introduce | transduce into the polymer the dimerization group which dimerizes.
共重合体の重合方法としては、溶液重合、塊状重合、乳化重合、懸濁重合等の公知の方法を用いることができ、例えば、単量体組成物を溶媒中で開始剤の存在下、重合反応させる方法を採用することができる。
前記重合反応に用いる溶媒としては、単量体組成物が溶解する溶媒であれば良く、例えば、水、メタノール、エタノール、プロパノール、ジメチルホルムアミド、ジメチルスルホキシド、テトラヒドロフラン、クロロホルム、ジクロロメタン、１，１，２，２-テトラクロロエタン又はこれら２種以上の混合液が挙げられる。
前記重合反応に用いる開始剤としては、通常の開始剤ならばいずれを用いてもよく、例えば、ラジカル重合の場合は脂肪族アゾ化合物や有機過酸化物を用いることができる。
得られた共重合体は、溶媒が水の場合は精製後、共重合体の濃度を調整することでそのまま光修復剤として用いることができる。溶媒が有機溶媒の場合は、アセトンによる再沈あるいは濾過精製することによって共重合体を単離した後、水に溶解させ、共重合体の濃度を調整することで光修復剤を得ることができる。
本発明に用いる水としては、精製水等を用いることができる。
As the polymerization method of the copolymer, known methods such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like can be used. For example, the monomer composition is polymerized in a solvent in the presence of an initiator. The method of making it react can be employ | adopted.
The solvent used in the polymerization reaction may be any solvent that dissolves the monomer composition. For example, water, methanol, ethanol, propanol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, chloroform, dichloromethane, 1,1,2 , 2-tetrachloroethane or a mixture of two or more of these.
Any initiator can be used as the initiator used in the polymerization reaction. For example, in the case of radical polymerization, an aliphatic azo compound or an organic peroxide can be used.
When the solvent is water, the obtained copolymer can be used as it is as a photorestoring agent by adjusting the concentration of the copolymer after purification. When the solvent is an organic solvent, the photorepairing agent can be obtained by isolating the copolymer by reprecipitation with acetone or filtering and then dissolving it in water and adjusting the concentration of the copolymer. .
As water used in the present invention, purified water or the like can be used.
（光修復剤）
本発明の「光修復剤」は、上記の本発明の重合体（又は共重合体）を含み、可逆的な光二量化反応を示すので、以下のような用途に使用することができるが、特に限定されない。
（１）表面処理剤。本発明の光修復剤を様々な表面（例、膜表面、船舶の船底等）に塗布することにより、ファウリング物質が吸着した表面を光照射により該物質を除去できる。
（２）生体材料保護剤。本発明の光修復剤を様々な生体材料（ステント等）に塗布することにより、血栓等が付着した生体材料を生体外からの光照射により該血栓等を除去できる。
（３）接着剤。本発明の光修復剤を様々な生体材料に塗布したのち、光照射により材料間を接着することができ、さらに接着部位への血栓等の付着を抑制できる。
加えて、本発明の光修復剤は、用途により、液相状態（例、溶液）、固相状態（例、フィルム）等のいずれでも良い。
(Light restoration agent)
The “photorestoring agent” of the present invention contains the above-described polymer (or copolymer) of the present invention and exhibits a reversible photodimerization reaction, and thus can be used for the following applications. It is not limited.
(1) Surface treatment agent. By applying the photorestoring agent of the present invention to various surfaces (eg, film surface, ship bottom, etc.), the surface on which the fouling material is adsorbed can be removed by light irradiation.
(2) Biomaterial protective agent. By applying the photorestoring agent of the present invention to various biomaterials (stents and the like), the thrombus and the like can be removed from the biomaterial to which the thrombus and the like are adhered by light irradiation from outside the living body.
(3) Adhesive. After applying the photorestoring agent of the present invention to various biomaterials, the materials can be adhered by light irradiation, and adhesion of thrombus or the like to the adhesion site can be suppressed.
In addition, the photorestoring agent of the present invention may be in a liquid phase state (eg, solution), a solid phase state (eg, film), or the like depending on the application.
（光修復剤が塗布された表面を有する材料）
本発明の「光修復剤が塗布された表面を有する材料」において、材料は特に限定されず、例えば、膜、船、生体材料等を例示することができる。
本発明の光修復剤が塗布された表面を有する材料は、光照射によるファウリング物質除去作用を有する。加えて、本発明の修復剤を、すでに本発明の光修復剤が塗布された表面に、追加添加することもできる。これにより、該材料は、長期間の光修復剤効果を有することができる。
(Material having a surface coated with a photo-restoring agent)
In the “material having a surface coated with a photorestoring agent” of the present invention, the material is not particularly limited, and examples thereof include membranes, ships, and biomaterials.
The material having the surface coated with the photorestoring agent of the present invention has a fouling substance removing action by light irradiation. In addition, the restorative agent of the present invention can be additionally added to a surface that has already been coated with the light restorative agent of the present invention. Thereby, the material can have a long-term photorepair agent effect.
以下、実施例を挙げて本発明を詳細に説明するが、本発明の範囲はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the scope of the present invention is not limited by these Examples.
（本発明の光修復剤の作製）
本発明の光修復剤に含まれる重合体を合成した。詳細は、以下の通りである。
(Preparation of photorestoring agent of the present invention)
A polymer contained in the photorestoring agent of the present invention was synthesized. Details are as follows.
（二量化基を含む単量体の合成）
下記のスキーム１に示す反応により、二量化基を含む単量体として重合性官能基を導入したクマリン誘導体の7-（2-メタクリロイルオキシ）クマリン（以後、MACと称する場合がある）を合成した。詳細は、以下の通りである。
(Synthesis of monomer containing dimerization group)
By the reaction shown in the following scheme 1, a coumarin derivative 7- (2-methacryloyloxy) coumarin (hereinafter sometimes referred to as MAC) having a polymerizable functional group introduced as a monomer containing a dimerization group was synthesized. . Details are as follows.
遮光のメスフラスコに7-ヒドロキシクマリン（13 g、0.08 mmol）とトリエチルアミン（8.1 g、0.08 mmol）を加え，ジクロロメタン（200 mL）に溶解した。その後、氷浴下でジクロロメタン（150 mL）に溶解した塩化メタクリロイル（8.6 g、0.08 mol）を少しずつ滴下し、一晩撹拌した。溶媒を減圧留去した後、クロロホルムに溶解し、水で３回洗浄した後、クロロホルムを減圧留去することで薄橙色の固体を得た。 得られた固体をメタノール（MeOH）/テトラヒドロフラン（THF） ｛MeOH/THF = 2/1 (v/v)｝により再結晶し、MACを得た。得られたMACの収率は36%であった。 7-hydroxycoumarin (13 g, 0.08 mmol) and triethylamine (8.1 g, 0.08 mmol) were added to a light-shielded volumetric flask and dissolved in dichloromethane (200 mL). Then, methacryloyl chloride (8.6 g, 0.08 mol) dissolved in dichloromethane (150 mL) was added dropwise in an ice bath, and the mixture was stirred overnight. After the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform and washed three times with water, and then chloroform was distilled off under reduced pressure to obtain a light orange solid. The obtained solid was recrystallized from methanol (MeOH) / tetrahydrofuran (THF) {MeOH / THF = 2/1 (v / v)} to obtain MAC. The yield of the obtained MAC was 36%.
（重合体の合成）
次に、下記のスキーム２に示す反応により、MACとＭＰＣを共重合することにより、本発明の重合体であるP(MAC-co-MPC)を合成した。詳細は、以下の通りである。
(Polymer synthesis)
Next, P (MAC-co-MPC), which is a polymer of the present invention, was synthesized by copolymerizing MAC and MPC by the reaction shown in Scheme 2 below. Details are as follows.
MAC（1.54 g、6.7 mmol）とＭＰＣ（1.98 g、6.7 mmol）およびアゾビスイソブチロニトリル（AIBN）（11 mg、0.067 mmol）をN,N-ジメチルホルムアミド（DMF）/メタノール混合溶液｛DMF/MeOH = 1/1 (v/v)｝に溶解し、アルゴン（Ar）雰囲気下で70℃、7時間撹拌した。得られた溶液は、氷冷下においてTHFに滴下することより再沈殿し、生成した沈殿を吸引ろ過により回収した後、３日間減圧乾燥し、クマリン基導入MPCポリマーであるP（MAC-co-MPC）を得た。
得られたP（MAC-co-MPC）の収率は81%であり、1H-NMR測定（AL-400、日本電子株式会社製）の結果、MACの導入率は42 mol%であった。
MAC (1.54 g, 6.7 mmol), MPC (1.98 g, 6.7 mmol) and azobisisobutyronitrile (AIBN) (11 mg, 0.067 mmol) in N, N-dimethylformamide (DMF) / methanol mixed solution {DMF / MeOH = 1/1 (v / v)} and stirred at 70 ° C. for 7 hours under an argon (Ar) atmosphere. The obtained solution was re-precipitated by adding dropwise to THF under ice-cooling, and the produced precipitate was collected by suction filtration, and then dried under reduced pressure for 3 days. P (MAC-co- MPC).
The yield of the obtained P (MAC-co-MPC) was 81%, and as a result of 1H-NMR measurement (AL-400, manufactured by JEOL Ltd.), the introduction rate of MAC was 42 mol%.
｛フィルム形状の本発明の光修復剤の作製｝
P(MAC-co-MPC)フィルムは、スピンキャストにより作製した（参照：図１）。詳細は、以下の通りである。
{Preparation of film-shaped photorestoring agent of the present invention}
The P (MAC-co-MPC) film was produced by spin casting (see: FIG. 1). Details are as follows.
合成したP（MAC-co-MPC）をメタノール/クロロホルム（CHCl3）混合溶媒｛MeOH/CHCl3 = 1/3 (v/v)｝に5wt% となるように溶解した。次に、基板となるシリコンウェハを1 cm角に成形し、超音波を当てながらメタノール、アセトンおよび水の順で10分ずつ洗浄した。さらに、シリコンウェハ上に P(MAC-co-MPC)溶液を40μL 滴下し、スピンコーター｛1H-D1、（株） ミカサ製｝を用いて、回転数2000 rpmで60秒間スピンキャストした。最後に、キャストしたポリマーにクマリンが光二量化反応を示す波長360 nmの光を6時間照射することにより光架橋P（MAC-co-MPC）フィルムを作製した。
なお、光照射はウシオ電機社製 SX-UI502HQ を用いて、 以下の条件で実施した。
ランプ：超高圧UV ランプ 500 W
照射距離：57cm
フィルター：シグマ光機製 VPF-50S-10-40-36000（360 nm）
また、同様の方法で石英ガラス上にもP（MAC-co-MPC）フィルムを作製した。
The synthesized P (MAC-co-MPC) was dissolved in a methanol / chloroform (CHCl 3 ) mixed solvent {MeOH / CHCl 3 = 1/3 (v / v)} so as to be 5 wt%. Next, a silicon wafer to be a substrate was formed into a 1 cm square, and washed with methanol, acetone, and water in this order for 10 minutes while applying ultrasonic waves. Further, 40 μL of P (MAC-co-MPC) solution was dropped on the silicon wafer, and spin-cast at a rotational speed of 2000 rpm for 60 seconds using a spin coater {1H-D1, manufactured by Mikasa Co., Ltd.}. Finally, the photopolymerized P (MAC-co-MPC) film was produced by irradiating the cast polymer with light having a wavelength of 360 nm where coumarin exhibits a photodimerization reaction for 6 hours.
The light irradiation was performed using the SX-UI502HQ manufactured by USHIO INC. Under the following conditions.
Lamp: Ultra high pressure UV lamp 500 W
Irradiation distance: 57cm
Filter: Sigma Koki VPF-50S-10-40-36000 (360 nm)
A P (MAC-co-MPC) film was also produced on quartz glass in the same manner.
｛本発明の光修復剤の可逆的な光二量化反応の確認｝
光修復剤が可逆的な光二量化反応を示すことを確認した。詳細は、以下の通りである。
{Confirmation of reversible photodimerization reaction of the photorestoring agent of the present invention}
It was confirmed that the photorestoring agent exhibited a reversible photodimerization reaction. Details are as follows.
光修復剤｛P（MAC-co-MPC）フィルム｝の可逆的な光二量化反応は、紫外可視分光光度計（UV-1800、（株）島津製作所）を用いて、UV-Vis測定により確認した。なお、UV-Vis 測定の際は、シリコンウェハは光を透過させないので、石英ガラス上に成膜したフィルムを用いた。
光照射機｛SX-UI502HQ、（株） ウシオ電機｝により所定時間360 nmと254 nmの光を実施例で作成したP(MAC-co-MPC) フィルムに照射した。なお、光照射は以下の条件で行った。
ランプ：超高圧UV ランプ 500 W
照射距離：57cm
フィルター：シグマ光機製VPF-50S-10-40-36000 （360nm）、VPF-50S-10-20-25400 （254nm）
The reversible photodimerization reaction of the photorestoring agent {P (MAC-co-MPC) film} was confirmed by UV-Vis measurement using an ultraviolet-visible spectrophotometer (UV-1800, Shimadzu Corporation). . In the UV-Vis measurement, the silicon wafer does not transmit light, so a film formed on quartz glass was used.
The P (MAC-co-MPC) film prepared in the example was irradiated with light of 360 nm and 254 nm for a predetermined time by a light irradiator {SX-UI502HQ, USHIO INC.}. In addition, light irradiation was performed on condition of the following.
Lamp: Ultra high pressure UV lamp 500 W
Irradiation distance: 57cm
Filter: VPF-50S-10-40-36000 (360nm), VPF-50S-10-20-25400 (254nm) made by Sigma Kogyo
（結果）
図２及び図３の結果から明らかなように、クマリンが光二量化反応を示す360 nm の波長光をP（MAC-co-MPC）フィルムに照射した際は、吸収が低下していることから、クマリンの二量化反応の進行が確認できた（参照：図２）。また、クマリンが光開裂反応を示す254 nmの波長光をP（MAC-co-MPC）フィルムに照射した際は、吸収が増加していることから、クマリン二量体の開裂反応の進行が確認できた（参照：図３）。
以上により、作製した P(MAC-co-MPC) フィルムは、クマリンの性質である可逆的な光二量化反応を示すことを確認した。
(result)
As is clear from the results of FIG. 2 and FIG. 3, when the P (MAC-co-MPC) film is irradiated with 360 nm wavelength light in which coumarin exhibits a photodimerization reaction, the absorption decreases. Progress of the dimerization reaction of coumarin was confirmed (see: FIG. 2). In addition, when the P (MAC-co-MPC) film was irradiated with light with a wavelength of 254 nm, where coumarin exhibits a photocleavage reaction, the absorption increased, confirming the progress of the coumarin dimer cleavage reaction. (Reference: FIG. 3).
From the above, it was confirmed that the produced P (MAC-co-MPC) film exhibited a reversible photodimerization reaction that is a property of coumarin.
（本発明の光修復剤の水中での特性の確認）
本発明の光修復剤の水中での安定性及び溶解性の変化を確認した。詳細は、以下の通りである。
(Confirmation of characteristics of the photorestoring agent of the present invention in water)
Changes in stability and solubility of the photorestoring agent of the present invention in water were confirmed. Details are as follows.
（本発明の光修復剤の水中での安定性の確認）
実施例１で作製したP(MAC-co-MPC)フィルムの水中での安定性を確認するために、分光エリプソメトリー（M-2000X-KMy, J. A. Woollam Co.） により膜厚変化を調べた。 膜厚変化は、水に浸漬する前のP(MAC-co-MPC) フィルムの膜厚を１とし、水に浸漬してから窒素ガスにより十分乾燥させて、エリプソメトリーにより測定した膜厚を規格化することにより示した。
(Confirmation of the stability of the photorestoring agent of the present invention in water)
In order to confirm the stability of the P (MAC-co-MPC) film prepared in Example 1 in water, the change in film thickness was examined by spectroscopic ellipsometry (M-2000X-KMy, JA Woollam Co.). The change in film thickness is defined as the film thickness measured by ellipsometry, assuming that the film thickness of P (MAC-co-MPC) film before being immersed in water is 1, which is immersed in water and sufficiently dried with nitrogen gas. It was shown by
（本発明の光修復剤の水中での安定性の確認結果）
所定の時間、水に浸漬した後の規格化した膜厚を図４に示す。図４の結果から明らかなように、MAC導入率42 mol%のP（MAC-co-MPC）フィルムでは、水に浸漬しても膜厚に大きな変化は見られなかったのに対して、MAC導入率30 mol%のフィルムでは、膜厚が大きく減少した。
(Confirmation result of stability of the photorestoring agent of the present invention in water)
FIG. 4 shows the normalized film thickness after immersion in water for a predetermined time. As is clear from the results in FIG. 4, the P (MAC-co-MPC) film with a MAC introduction rate of 42 mol% did not show a significant change in film thickness even when immersed in water. In the film with an introduction rate of 30 mol%, the film thickness decreased greatly.
（本発明の光修復剤の光照射による水への溶解性の変化の確認）
光架橋PMAC フィルムおよび光架橋 P(MAC-co-MPC)フィルムを水に浸漬した際の膜厚を測定し、続いてクマリン二量体が開裂する254 nmの波長光を5分間照射した後に水に浸漬した際の膜厚を測定することにより、光照射による水への溶解性の変化を調べた。なお、光照射は実施例２と同一の条件で行った。
(Confirmation of change in solubility in water by light irradiation of the photorestoring agent of the present invention)
The film thickness when the photocrosslinked PMAC film and photocrosslinked P (MAC-co-MPC) film were immersed in water was measured, followed by irradiation with 254 nm wavelength light that cleaves the coumarin dimer for 5 minutes. By measuring the film thickness when immersed in water, the change in solubility in water by light irradiation was examined. The light irradiation was performed under the same conditions as in Example 2.
（本発明の光修復剤の光照射による水への溶解性の変化の確認結果）
クマリン二量体が開裂する254 nmの波長光の照射前後の水に浸漬した際の膜厚を図５に示した。なお、膜厚はフィルムを水中からとりだし、窒素ガスにより十分乾燥させてからエリプソメトリーにより測定した。図５の結果から明らかなように、PMACフィルムおよびP(MAC-co-MPC)フィルムのいずれの場合もクマリンが二量体を形成した状態では、膜厚に大きな変化は認められなかった。しかし、それらのフィルムに254 nmの波長光を照射した後に水に浸漬すると、浸漬時間の増加に伴い、P(MAC-co-MPC) フィルムでは、膜厚の減少が確認できた。
(Confirmation result of solubility change in water by light irradiation of photorestoring agent of the present invention)
The film thickness when immersed in water before and after irradiation with light having a wavelength of 254 nm at which the coumarin dimer is cleaved is shown in FIG. The film thickness was measured by ellipsometry after the film was taken out of water and sufficiently dried with nitrogen gas. As is clear from the results in FIG. 5, no significant change in the film thickness was observed in the state where the coumarin formed a dimer in both cases of the PMAC film and the P (MAC-co-MPC) film. However, when the films were immersed in water after irradiating light with a wavelength of 254 nm, it was confirmed that the film thickness decreased in the P (MAC-co-MPC) film as the immersion time increased.
以上の結果より、本発明の光修復剤であるP(MAC-co-MPC)フィルムは、クマリンの二量化状態により、水への溶解性が変化することが確認できた。その際、MAC導入量が30 mol%程度では、クマリンを二量化しても短時間で水に溶解し、一方MAC導入量が100 mol%になると、254 nmの光を照射しても、水に溶解しないことが明らかとなった。加えて、MAC導入率42 mol%付近のフィルムが360 nmの光照射によって水への溶解性が低下し、254 nmの光照射により、表面を溶解させて表面性質を回復できることを確認した。
以上により、本発明の光修復剤であるP(MAC-co-MPC)フィルムでは、クマリン基とＭＰＣの構成単位のモル比が、４０〜５０：６０〜５０であることが好ましい。
From the above results, it was confirmed that the solubility of the P (MAC-co-MPC) film, which is the photorestoring agent of the present invention, varies depending on the dimerization state of coumarin. At that time, when the MAC introduction amount is about 30 mol%, even if the coumarin is dimerized, it dissolves in water in a short time.On the other hand, when the MAC introduction amount becomes 100 mol%, the water is irradiated even when irradiated with 254 nm light. It was clarified that it does not dissolve. In addition, it was confirmed that the film with a MAC introduction rate of around 42 mol% was poorly soluble in water when irradiated with light of 360 nm, and the surface properties could be recovered by irradiating with light of 254 nm.
As described above, in the P (MAC-co-MPC) film that is the photorestoring agent of the present invention, the molar ratio of the coumarin group and the constituent unit of MPC is preferably 40-50: 60-50.
｛本発明の光修復剤のクリーニング性能の確認｝
本発明の光修復剤が、光照射によるクリーニング性能を示すことを確認した。詳細は、以下の通りである。
{Confirmation of cleaning performance of photorestorant of the present invention}
It was confirmed that the photorestoring agent of the present invention exhibits cleaning performance by light irradiation. Details are as follows.
実施例１で作製したP(MAC-co-MPC)フィルムの光照射によるクリーニング性能は、蛍光顕微鏡｛DP70、（株）OLYMPUS｝での観察により行った。
倍率：４倍
ISO感度：800
露光時間：826.8 ms
励起：465-490 nmのフィルターを用いた。
なお、光照射は実施例２と同一の条件で行った。
The cleaning performance by light irradiation of the P (MAC-co-MPC) film prepared in Example 1 was observed by observation with a fluorescence microscope {DP70, OLYMPUS}.
Magnification: 4 times
ISO sensitivity: 800
Exposure time: 826.8 ms
Excitation: A 465-490 nm filter was used.
The light irradiation was performed under the same conditions as in Example 2.
（結果）
360 nmの光照射による架橋 P（MAC-co-MPC）フィルムを、フルオレセインイソチオシアネート（FITC）で蛍光標識化したウシ血清アルブミン（BSA-FITC）が溶解した緩衝液に浸漬した時、さらにそれに254 nmの光を照射したときのフィルム表面の蛍光顕微鏡写真を図６に示す。
より詳しくは、図６(a)は、P(MAC-co-MPC) フィルムの蛍光顕微鏡画像であり、図６(b)は、BSA-FITC溶液に7日浸漬した後にリン酸緩衝液（pH7.4）で洗浄した蛍光顕微鏡画像であり、図６(c)は、さらに、クマリン二量体が開裂する254 nmの波長光を5分間照射した後にリン酸緩衝液（pH7.4）で洗浄した蛍光顕微鏡画像である。
図６の画像から明らかなように、BSA-FITC溶液に浸漬した P(MAC-co-MPC) フィルムには、タンパク質の吸着が確認でき、さらに254 nmの光照射の後に洗浄を行うことにより、吸着していたタンパク質が除去できた。
(result)
When cross-linked P (MAC-co-MPC) film by irradiation with 360 nm light was immersed in a buffer solution in which bovine serum albumin (BSA-FITC) fluorescently labeled with fluorescein isothiocyanate (FITC) was dissolved, 254 FIG. 6 shows a fluorescence micrograph of the film surface when irradiated with light of nm.
More specifically, FIG. 6 (a) is a fluorescence microscope image of a P (MAC-co-MPC) film, and FIG. 6 (b) is a phosphate buffer solution (pH 7) after being immersed in a BSA-FITC solution for 7 days. Fig. 6 (c) shows the fluorescence microscope image washed in .4). Fig. 6 (c) is further washed with phosphate buffer solution (pH 7.4) after irradiating with 254 nm wavelength light that cleaves the coumarin dimer for 5 minutes. It is the acquired fluorescence microscope image.
As is clear from the image in FIG. 6, the P (MAC-co-MPC) film immersed in the BSA-FITC solution can confirm the adsorption of protein, and further, after washing after irradiation with light at 254 nm, The adsorbed protein could be removed.
以上の結果から、本発明の光修復剤は、表面に吸着したタンパク質を光照射により除去できる特性を有する。これにより、本発明の光修復剤は、分離膜や生体材料の長寿命化に利用することができる。 From the above results, the photorestoring agent of the present invention has the property that the protein adsorbed on the surface can be removed by light irradiation. Thereby, the photorestoration agent of this invention can be utilized for the lifetime improvement of a separation membrane or a biomaterial.
表面に吸着したタンパク質等のファウリング物質を光照射により除去できる光修復剤を提供することができる。 It is possible to provide a photorestoring agent capable of removing fouling substances such as proteins adsorbed on the surface by light irradiation.
Claims (7)
A photorestoring agent comprising a polymer obtained by polymerizing a monomer in which dimerization groups that dimerize upon irradiation with light are introduced into the following formula (1).
The polymer is a copolymer obtained by copolymerizing a monomer containing a dimerization group that dimerizes with each other when irradiated with light and a monomer represented by the formula (1). The photorestoration agent according to 1.
The photorestoration agent according to claim 1 or 2, wherein the dimerization group is at least one substituent selected from the group consisting of a coumarin group, a cinnamoyl group, a thymine group, a uracil group, and an anthracene group.
The monomer containing the dimerization group is 7- (2-methacryloyloxycoumarin), and the monomer represented by the formula (1) is 2-methacryloyloxyethyl phosphorylcholine. The photorestoration agent of any one.
The light according to any one of claims 1 to 4, wherein a molar ratio of the structural unit of the dimerization group and the structural unit of the monomer represented by the formula (1) is 20 to 90:80 to 10. Repair agent.
（１）表面処理剤
（２）生体材料保護剤
（３）接着剤
The photorestoring agent according to any one of claims 1 to 5, wherein the photorestoring agent is any one of the following uses.
(1) Surface treatment agent (2) Biomaterial protective agent (3) Adhesive
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| JP2006239636A (en) * | 2005-03-04 | 2006-09-14 | Kazuhiko Ishihara | Fouling prevention material and separation membrane having surface treated with the fouling prevention material |
| JP2011523452A (en) * | 2008-04-16 | 2011-08-11 | スマート ホログラムズ リミテッド | Photopolymerizable composition |
| JP2012144610A (en) * | 2011-01-11 | 2012-08-02 | Kansai Univ | Photoresponsive polymer and molded object made by forming the photoresponsive polymer, and its usage |
| JP2014008479A (en) * | 2012-07-02 | 2014-01-20 | Kobe Univ | Surface treatment agent for polyamide reverse osmosis membrane |
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| JP2006239636A (en) * | 2005-03-04 | 2006-09-14 | Kazuhiko Ishihara | Fouling prevention material and separation membrane having surface treated with the fouling prevention material |
| JP2011523452A (en) * | 2008-04-16 | 2011-08-11 | スマート ホログラムズ リミテッド | Photopolymerizable composition |
| JP2012144610A (en) * | 2011-01-11 | 2012-08-02 | Kansai Univ | Photoresponsive polymer and molded object made by forming the photoresponsive polymer, and its usage |
| JP2014008479A (en) * | 2012-07-02 | 2014-01-20 | Kobe Univ | Surface treatment agent for polyamide reverse osmosis membrane |
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| WO2021157668A1 (en) * | 2020-02-07 | 2021-08-12 | 国立研究開発法人物質・材料研究機構 | Polymer compound, method for producing polymer compound, adhesive composition, cured product, method for producing adhesive composition, and method for adjusting adhesive strength |
| JPWO2021157668A1 (en) * | 2020-02-07 | 2021-08-12 |
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