JP2017186536A - Photoreactive polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreactive polymer capable of effectively and simply conducting a hydrophilization treatment of a hydrophobic substrate surface with less damage to a substrate.SOLUTION: The photoreactive polymer is a polymer having a functional group having hydrophilicity and a functional group high in photoreactivity in a side chain.SELECTED DRAWING: None

Description

  The present invention relates to a photoreactive polymer that hydrophilizes the surface of a hydrophobic substrate.

  In order to impart functions such as antifogging or antifouling properties, antistatic properties, and biocompatibility to the surface, surface hydrophilization of hydrophobic substrates is widely used. As the method, a method of generating a hydrophilic functional group on the surface of a hydrophobic polymer substrate, such as plasma treatment, glow discharge treatment, ion etching, etc., or coating of a surfactant on the substrate surface or a substrate A method such as direct kneading has been used (for example, see Non-Patent Document 1). However, these methods have problems in that the substrate is damaged under severe conditions and it is difficult to permanently retain the hydrophilic surface.

  On the other hand, a method of hydrophilizing a hydrophobic polymer substrate surface using a photoreactive polymer has also been proposed (see Patent Documents 1 and 2). These methods are efficient and simple. However, the reactivity of the photoreactive group used is low, and uniform hydrophilicity cannot be achieved unless ultraviolet rays are irradiated with high intensity for a relatively long time. If it is weak, it has a problem that the substrate is damaged by ultraviolet irradiation.

Japanese Patent Publication No. 3-505979 JP 2010-59346 A

Koichi Ochi, Surface Analysis / Modification Chemistry (Edited by the Adhesion Society of Japan), Nikkan Kogyo Shimbun, 2003, 97-145

  An object of the present invention is to provide a photoreactive polymer capable of hydrophilizing a hydrophobic (base material) surface, which is efficient and simple, has little damage to the base material, and a surface modifier containing the same. It is to provide.

  The present inventor has intensively studied to solve the above problems. As a result, by finding a photoreactive polymer having a functional group having hydrophilicity and a functional group having high photoreactivity in the side chain, and using the photoreactive polymer, the surface of the hydrophobic polymer substrate is obtained. Has been found to be hydrophilic, and the present invention has been completed.

That is, the present invention is as follows.
[1] A photoreactive polymer having a structure represented by the following general formula (1) and having a number average molecular weight of 1,000 to 1,000,000.

（式中、ｍ及びｎは互いに独立して１以上の整数を表し、Ｘは置換基を有しても良いフェニレン基、又は、エステル結合若しくはアミド結合で示される基を表し、Ｙはベタイン性基、アルコキシアルキル基、アルコキシポリオキシエチレン基、ヒドロキシポリオキシエチレン基から選ばれた親水性基を表し、Ｚは−Ｏ−又は−Ｎ（Ｒ_３）−で示される基を表し、Ａは−Ｏ−又は−ＣＨ_２−で示される基を表し、Ｒ_１、Ｒ_２及びＲ_３は互いに独立して水素原子又はＣ_１〜Ｃ_６の炭化水素基を表し、Ｒ_４はＣ_３〜Ｃ_６の２価の炭化水素基を表し、Ｒ_５はフッ素原子を表し、ｐは０〜４の整数を表す。）
［２］下記一般式（２）で示される構造を有する［１］に記載の光反応性ポリマー。

(In the formula, m and n each independently represent an integer of 1 or more, X represents a phenylene group which may have a substituent, or a group represented by an ester bond or an amide bond, and Y represents a betaine property. Represents a hydrophilic group selected from a group, an alkoxyalkyl group, an alkoxypolyoxyethylene group, and a hydroxypolyoxyethylene group, Z represents a group represented by —O— or —N (R ₃ ) —, and A represents — Represents a group represented by O— or —CH ₂ —, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a C _{1 to} C ₆ hydrocarbon group, and R ₄ represents C _{3 to} C _6. And R ₅ represents a fluorine atom, and p represents an integer of 0 to 4.)
[2] The photoreactive polymer according to [1], which has a structure represented by the following general formula (2).

（式中、ｍ、ｎ、Ｚ、Ａ、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５及びｐは前記と同じ意味を表す。ｒの値は２〜９０の整数を表す。）
［３］下記一般式（３）で示される構造を有する［１］に記載の光反応性ポリマー。

(In the formula, m, n, Z, A, R ₁ , R ₂ , R ₄ , R ₅ and p represent the same meaning as described above. The value of r represents an integer of 2 to 90.)
[3] The photoreactive polymer according to [1], which has a structure represented by the following general formula (3).

（式中、ｍ及びｎは互いに独立して１以上の整数を表し、ｒの値は２〜９０の整数を表し、Ｒ_４はＣ_３〜Ｃ_６の２価の炭化水素基を表す。）
［４］ｍ／（ｍ＋ｎ）の値が０．０２〜０．７である［１］〜［３］のいずれか１項に記載の光反応性ポリマー。

(In the formula, m and n each independently represent an integer of 1 or more, r represents an integer of 2 to 90, and R ₄ represents a C _{3 to} C ₆ divalent hydrocarbon group.)
[4] The photoreactive polymer according to any one of [1] to [3], wherein a value of m / (m + n) is 0.02 to 0.7.

Hereinafter, the present invention will be described in detail.
Although it does not specifically limit as a substituent of the phenylene group which may have a substituent represented by X, For example, an alkyl group (For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec- Butyl group, tert-butyl group etc.), alkoxy group (eg methoxy group, ethoxy group, propoxy group, isopropoxy group etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group , Amino group, hydroxy group and the like. X is preferably an ester bond.

  Examples of the hydrophilic group represented by Y include a betaine group, an alkoxyalkyl group, an alkoxypolyoxyethylene group, and a hydroxypolyoxyethylene group. In the present invention, the term “betaine” means that a portion having a positive charge and a portion having a negative charge in an ionized state are not adjacent to each other in the same group and can be dissociated into atoms having a positive charge. It means that the atoms are not bonded and are neutral as a whole (has no charge). The betaine group is not particularly limited, and examples thereof include a carbobetaine group, a sulfobetaine group, a phosphobetaine group, and an amide betaine group. Although it does not specifically limit as an alkoxyalkyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group is illustrated. The alkoxy polyoxyethylene group is not particularly limited, and examples thereof include a methoxy polyoxyethylene group, an ethoxy polyoxyethylene group, a normal propoxy polyoxyethylene group, and an isopropoxy polyoxyethylene group. An oxyethylene group is preferred.

R _{1, R 2} and is not particularly restricted but includes hydrocarbon groups _C 1 -C ₆ represented by _{R 3,} methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, neopentyl group, isopentyl group, 1-methylbutyl group, 1-ethylpropyl group, cyclobutylmethyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, Examples include 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, cyclohexyl group, and phenyl group.

The C _{3 to} C ₆ divalent hydrocarbon group represented by R ₄ is not particularly limited, but — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — Examples include (CH ₂ ) _6- , a phenylene group, and the like. If the carbon number of the divalent hydrocarbon group represented by R ₄ is 2 or less, the glass transition temperature of the photoreactive polymer is increased and the molecular mobility of the side chain is decreased. Is consumed in the crosslinking reaction between the photoreactive polymers rather than the reaction with the base material, and the photoreactive polymer immobilization rate on the surface of the base material is decreased. On the other hand, when the carbon number of the divalent hydrocarbon group represented by R ₄ exceeds 6, the concentration of the azide group in the photoreactive polymer is lowered, the number of crosslinking points is reduced, and the photoreactive polymer on the substrate surface is reduced. Since the immobilization rate is lowered, it is not preferable.

  In the photoreactive polymer having the structure represented by the general formula (1), m and n each independently represent an integer of 1 or more. Here, the value of m / (m + n) is preferably 0.02 to 0.7, and more preferably 0.05 to 0.5. If it is this range, it is excellent at the point of coexistence of the adhesiveness to a base material, and the protein adsorption | suction suppression effect.

  The following general formula (4) included in the general formula (1)

（式中、Ｒ_１、Ｘ、Ｙ及びｎは前記と同じ意味を表す。）で表される構造単位としては、特に限定されないが、ポリエチレングリコールメチルエーテルメタクリレート、ポリエチレングリコールメタクリレート、ポリエチレングリコールメチルエーテルアクリレート、ポリエチレングリコールアクリレート、２−ヒドロキシエチルメタクリレート、２−メタクリロイルオキシエチルホスホリルコリン、２−アクリロイルオキシエチルホスホリルコリン、［２−（メタクリロイルオキシ）エチル］ジメチル−（３−スルホプロピル）アンモニウムヒドロキシド、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン等のモノマーに由来する構造単位が例示され、タンパク質吸着抑制効果の点から、ポリエチレングリコールメチルエーテルメタクリレートや２−メタクリロイルオキシエチルホスホリルコリン、［２−（メタクリロイルオキシ）エチル］ジメチル−（３−スルホプロピル）アンモニウムヒドロキシド、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタインに由来する構造単位が好ましい。

The structural unit represented by (wherein R ₁ , X, Y and n represent the same meaning as described above) is not particularly limited, but polyethylene glycol methyl ether methacrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate , Polyethylene glycol acrylate, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, 2-acryloyloxyethyl phosphorylcholine, [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide, N-methacryloyloxy Examples of structural units derived from monomers such as ethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, etc. Polyethylene glycol methyl ether methacrylate, 2-methacryloyloxyethyl phosphorylcholine, [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide, N-methacryloyloxyethyl-N, N-dimethylammonium-α A structural unit derived from -N-methylcarboxybetaine is preferred.

  The following general formula (5) included in the general formula (1)

（式中、Ｒ_２、Ｒ_４、Ｒ_５、Ａ、Ｚ、ｍ及びｐは前記と同じ意味を表す。）で表される構造単位としては、特に限定されないが、３−（４−アジドフェノキシ）プロピルメタクリレート、４−（４−アジドフェノキシ）ブチルメタクリレート、５−（４−アジドフェノキシ）ペンチルメタクリレート、６−（４−アジドフェノキシ）ヘキシルメタクリレート、３−（４−アジド−２，３，５，６−テトラフルオロフェノキシ）プロピルメタクリレート、４−（４−アジドフェニル）ブチルメタクリレート、４−（４−アジド−２，３，５，６−テトラフルオロフェニル）ブチルメタクリレート、３−（４−アジドフェノキシ）プロピルアクリレート、４−（４−アジドフェニル）ブチルアクリレート、３−（４−アジドフェノキシ）プロピルメタクリルアミド、３−（４−アジド−２，３，５，６−テトラフルオロフェノキシ）プロピルメタクリルアミド、３−（４−アジドフェノキシ）プロピルアクリルアミド、４−（４−アジドフェニル）ブチルメタクリルアミド、４−（４−アジドフェニル）ブチルアクリルアミド等のモノマーに由来する構造単位が例示され、アジドの光分解速度の点から、３−（４−アジドフェノキシ）プロピルメタクリレートに由来する構造単位が好ましい。

The structural unit represented by (wherein R ₂ , R ₄ , R ₅ , A, Z, m and p have the same meaning as described above) is not particularly limited, but 3- (4-azidophenoxy) ) Propyl methacrylate, 4- (4-azidophenoxy) butyl methacrylate, 5- (4-azidophenoxy) pentyl methacrylate, 6- (4-azidophenoxy) hexyl methacrylate, 3- (4-azido-2,3,5, 6-tetrafluorophenoxy) propyl methacrylate, 4- (4-azidophenyl) butyl methacrylate, 4- (4-azido-2,3,5,6-tetrafluorophenyl) butyl methacrylate, 3- (4-azidophenoxy) Propyl acrylate, 4- (4-azidophenyl) butyl acrylate, 3- (4-azidophenoxy) pro Methacrylamide, 3- (4-azido-2,3,5,6-tetrafluorophenoxy) propyl methacrylamide, 3- (4-azidophenoxy) propyl acrylamide, 4- (4-azidophenyl) butyl methacrylamide, Examples include structural units derived from monomers such as 4- (4-azidophenyl) butylacrylamide, and structural units derived from 3- (4-azidophenoxy) propyl methacrylate are preferred from the viewpoint of the photodegradation rate of azide.

  The arrangement of the structural unit represented by the general formula (4) and the structural unit represented by the general formula (5) is not particularly limited, and may be any order of random, block, and alternating.

  The number average molecular weight of the photoreactive polymer having the structure represented by the general formula (1) can be selected in the range of 1,000 to 1,000,000, but the viscosity and solubility during coating, and the mechanical strength of the polymer layer In view of the above, the range of 10,000 to 500,000 is preferable. Further, the polydispersity (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, but for example, adhesion to a hydrophobic substrate. From the viewpoint of the stability of the coating film, about 1 to 5 is preferable.

  The photoreactive polymer having the structure represented by the general formula (1) may have a structural unit derived from another monomer without departing from the effect of the present invention. The structural units derived from other monomers are not particularly limited, but polystyrene, poly (α-methylstyrene), polyvinyl benzyl chloride, polyvinyl aniline, sodium polystyrene sulfonate, polyvinyl benzoic acid, polyvinyl phosphoric acid, polyvinyl pyridine, polydimethyl. Styrenic polymers such as aminomethylstyrene and polyvinylbenzyltrimethylammonium chloride; polyolefins such as polyethylene, polypropylene, polybutadiene, polybutene, and polyisoprene; poly (halogenated olefins) such as polyvinyl chloride, polyvinylidene chloride, and polytetrafluoroethylene; Polyvinyl esters such as polyvinyl acetate and polyvinyl propionate, and saponified polyvinyl alcohol, such as polyacrylonitrile (Meth) acrylic polymers such as polymethacrylic acid, polyperfluoroalkyl methacrylate, polyethyl acrylate, polyacrylic acid, polydimethylaminoethyl acrylate; polyacrylamide, polymethacrylamide, polydimethylaminopropyl acrylamide, And (meth) acrylamide polymers and the like.

  As for the photoreactive polymer of this invention, what is a photoreactive polymer which has a structure shown by General formula (6) is mentioned, for example.

（式中、ｍ、ｎ、ｒ及びＲ_４は前記と同じ意味を表す。）
ｒの値は、重合の進行しやすさから、２〜２０の範囲の整数が好ましい。Ｒ_４は、−（ＣＨ_２）_３−または−（ＣＨ_２）_４−であることが好ましく、更に好ましくは−（ＣＨ_２）_３−である。

(In the formula, m, n, r and R ₄ have the same meaning as described above.)
The value of r is preferably an integer in the range of 2 to 20 from the ease of polymerization. R ₄ is preferably — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, more preferably — (CH ₂ ) ₃ —.

  The photoreactive polymer having the structure represented by the general formula (1) can be produced by a conventional method basically based on the technical level of those skilled in the art, including preparation of monomer compounds and polymerization thereof. For example, the monomer used is not particularly limited, but polyethylene glycol methyl ether methacrylate, polyethylene glycol methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol acrylate, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, 2-acryloyloxyethyl. Has a hydrophilic group such as phosphorylcholine, [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine Monomer, 3- (4-azidophenoxy) propyl methacrylate, 4- (4-azidophenoxy) butyl Tacrylate, 5- (4-azidophenoxy) pentyl methacrylate, 6- (4-azidophenoxy) hexyl methacrylate, 3- (4-azido-2,3,5,6-tetrafluorophenoxy) propyl methacrylate, 4- (4 -Azidophenyl) butyl methacrylate, 4- (4-azido-2,3,5,6-tetrafluorophenyl) butyl methacrylate, 3- (4-azidophenoxy) propyl acrylate, 4- (4-azidophenyl) butyl acrylate , 3- (4-azidophenoxy) propyl methacrylamide, 3- (4-azido-2,3,5,6-tetrafluorophenoxy) propyl methacrylamide, 3- (4-azidophenoxy) propyl acrylamide, 4- ( 4-Azidophenyl) butylmethacrylamide Monomer having a photoreactive group such as 4- (4-azidophenyl) butylacrylamide is used.

  The polymerization is not particularly limited, and examples thereof include radical polymerization, ionic polymerization, and coordination polymerization. From the viewpoint of ease of operation, radical polymerization, particularly free radical polymerization or living radical polymerization is preferably used. The polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert Known radical initiators such as -butyl peroxypivalate, tert-butyl peroxydiisobutyrate, persulfate or persulfate-bisulfite can be used. As a polymerization solvent, for example, a known radical polymerization solvent such as water, THF, dioxane, acetone, 2-butanone, ethyl acetate, isopropyl acetate, benzene, toluene, DMF, DMSO, methanol, ethanol, isopropanol or a mixture thereof is used. For example, it can be manufactured by diluting the monomer concentration to 0.01 to 5 mol / L and the polymerization initiator concentration to 1 to 100 mmol / L and reacting at 0 to 80 ° C. for 1 to 72 hours. . Moreover, there is no restriction | limiting in particular as a superposition | polymerization form, For example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization is illustrated, and solution polymerization is preferably used from the simplicity of operation.

  The photoreactive polymer of the present invention can be used for various surface modifications such as surface hydrophilization and protein adsorption suppression. Details of the method of using the photoreactive polymer of the present invention will be described later.

  According to the present invention, it is possible to provide a photoreactive polymer that is efficient and simple and excellent in durability and capable of suppressing hydrophilicity and protein adsorption on the surface of a hydrophobic substrate.

  The photoreactive polymer of the present invention can hydrophilize the surface of various hydrophobic polymer substrates efficiently and simply.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

In the following examples, each physical property was measured and evaluated by the following methods.
(1) Obtained by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) spectrum analysis using a photoreactive polymer composition ratio nuclear magnetic resonance measuring apparatus (manufactured by JEOL, JNM-ECZ400S). It measured using d-chloroform as a heavy solvent.

(2) Physical properties of the photoreactive polymer The weight average molecular weight (Mw), number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the photoreactive polymer are determined by gel permeation. Measured by chromatography (GPC). Tosoh HLC-8320GPC was used as the GPC device, Tosoh TSKgel GMH _HR- L was used as the column, the column temperature was set to 40 ° C., and THF was used as the eluent. Using Tosoh monodisperse polystyrene as a standard sample, the molecular weight was converted in terms of polystyrene.

(3) Immobilization amount analysis of photoreactive polymer It measured using the Fourier-transform infrared spectrophotometer (FT-IR) (The product made by Perkin Elmer, SPECTRUM ONE). The relative intensity calculated from the photocarbonyl ^- derived ester carbonyl peak (around 1730 cm ⁻¹ ) intensity ÷ PVDF-derived peak intensity around 870 cm ⁻¹ was determined.

(4) The effect of immobilizing the hydrophilic photoreactive polymer on the hydrophilicity of the substrate was evaluated by measuring the underwater contact angle. This contact angle measurement was evaluated by a water contact angle (180-θ) obtained from a contact angle θ measured using a captive bubble method in which bubbles are brought into contact with the film surface in water. In actual measurement, after the measurement sample was immersed in pure water overnight, a contact angle meter was used to bring bubbles into contact with the surface in water at room temperature and normal pressure, and the contact angle was measured.

Reference Example 1 [Synthesis of 3- (4-azidophenoxy) propyl methacrylate]
4-Bromophenol (51.9 g, 0.30 mol) and potassium carbonate (97.6 g, 0.75 mol) were placed in a 500 mL eggplant-shaped flask and purged with argon. Dehydrated DMF (300 mL) was added, and the mixture was stirred with heating at 80 ° C. for 30 min. 3-Bromo-1-propanol (50.0 g, 0.36 mol) was added thereto, and the mixture was stirred with heating at 80 ° C. for 20 hours. After confirming the consumption of 4-bromophenol by TLC (hexane: ethyl acetate = 2: 1), the mixture was cooled to room temperature. Water (400 mL) was added and the organic phase was extracted with ethyl acetate (300 mL × 3). The organic phase was dried over magnesium sulfate, and then the solvent was distilled off to obtain 3- (4-bromophenyl) -1-propanol as a brown oil (66.4 g, 0.29 mol, 96%). ¹
1 H NMR (400 MHz, CDCl ₃ , rt): δ 1.72 (s, 1H), 2.00-2.07 (m, 2H), 3.83-3.89 (m, 2H), 4.09 (t, 2H, J = 6.0 Hz), 6.75-6.81 (m, 2H), 7.35-7.39 (m, 2H).

In a 500 mL eggplant-shaped flask, 3- (4-bromophenyl) -1-propanol (68.6 g, 0.30 mol), copper iodide (5.64 g, 29.6 mmol), sodium L-ascorbate (2.95 g 14) 0.9 mmol), N, N′-dimethylethylenediamine (4.80 mL, 44.7 mmol) was added and dissolved in ethanol (210 mL) and water (90 mL). After replacing the reaction vessel with Ar, sodium azide (34.6 g, 0.54 mol) was added and the mixture was heated to reflux for 5 hours. After confirming the consumption of 3- (4-bromophenyl) -1-propanol by TLC (hexane: ethyl acetate = 1: 1), the mixture was cooled to room temperature. After adding saturated brine (200 mL), the organic solvent was distilled off with an evaporator. The organic phase was extracted with ethyl acetate (200 mL × 3). The organic phase was dried over magnesium sulfate and the solvent was distilled off. The resulting black oil was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to give 3- (4-azidophenyl) -1-propanol as a brown oil (42.3 g, 0. 22 mol, 73%). ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 1.67-1.72 (br, 1H), 2.05 (quant like tt, 2H, J = 6.0, 6.0 Hz), 3.83--3.91 (m, 2H), 4.11 (t, 2H, J = 6.0 Hz), 6.87-6.92 (m, 2H), 6.93-6.98 ( m, 2H).
In a 500 mL eggplant-shaped flask, 3- (4-azidophenyl) -1-propanol (42.3 g, 0.22 mol), methacrylic acid (22.7 g, 0.26 mol), 4-dimethylaminopyridine (26.8 g, 0) .22 mol) was added, and the mixture was dissolved in methylene chloride (400 mL) after argon substitution. The reaction vessel was stirred in an ice bath at 0 ° C. for 30 minutes, DCC (56.2 g, 0.27 mol) was added, and the mixture was stirred as it was at 0 ° C. for 30 minutes. The ice bath was removed and stirred at room temperature for 21 hours. After confirming the consumption of 3- (4-azidophenyl) -1-propanol by TLC (hexane: ethyl acetate = 3: 1), the precipitated dicyclohexylurea was removed by Celite filtration, and the solid was washed with ethyl acetate (500 mL). did. The filtrate was concentrated, and the resulting crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give 3- (4-azidophenoxy) propyl methacrylate as a brown oil (29 .9 g, 0.11 mol, 52%). ¹ H NMR (400 MHz, CDCl ₃ , rt): δ 1.94 (s, 3H), 2.16 (quant like tt, 2H, J = 6.0, 6.0 Hz), 4.04 (T, 2H, J = 6.0 Hz), 4.34 (t, 2H, J = 6.0 Hz), 5.57 (t, 1H, J = 1.6 Hz), 6.09-6.12 (Br, 1H), 6.85-6.91 (m, 2H), 6.9
2-6.97 (m, 2H).

Reference Example 2 [Synthesis of 3- (4-azido-2,3,5,6-tetrafluorophenoxy) propyl methacrylate]
The reaction was conducted in the same manner as in Reference Example 1 except that pentafluorophenol (55.2 g, 0.3 mol) was used instead of 4-bromophenol, and 3- (4-azido-2,3,5, 6-Tetrafluorophenoxy) propyl methacrylate was obtained as a yellow oil (30.1 g, 0.09 mol, Total yield 30%). ¹ H-NMR (400 MHz, CDCl ₃ , rt.): Δ 1.94 (s, 3H), 2.16 (quant like tt, 2H, J = 6.0, 6.0 Hz), 4. 04 (t, 2H, J = 6.0 Hz), 4.34 (t, 2H, J = 6.0 Hz), 5.57 (t, 1H, J = 1.6 Hz), 6.09-6. 12 (br, 1H).

Reference Example 3 [Synthesis of 4- (4-azidophenyl) butyl methacrylate]
A 0.25M diethyl ether solution (300 ml, 0.075 mol) of 4-bromobenzylmagnesium bromide was poured into a 500 ml eggplant-shaped flask under nitrogen, cooled to −30 ° C., and then oxetane (13.1 g, 0.225 mol) and iodine. Copper (I) chloride (1.5 g, 0.008 mol) was added. Thereafter, the temperature was gradually raised and the reaction was allowed to proceed at room temperature for 20 hours. After completion of the reaction, water was added, the organic layer was extracted with ethyl acetate, and the extracted organic layer was dried over magnesium sulfate, and then the organic layer was distilled off to obtain a brown oily target product (8.9 g, 0.039 mol, 52%). ¹ H-NMR (400 MHz, CDCl ₃ , rt): δ 1.56-1.68 (m, 5H), 2.62 (m, 2H), 3.62 (m, 2H), 6. 75-6.81 (m, 2H), 7.35-7.39 (m, 2H).

The reaction was carried out in the same manner as in Reference Example 1 except that 4- (4-bromophenyl) -1-butanol was used instead of 3- (4-bromophenyl) -1-propanol. Product was obtained (5.5 g, 0.029 mol, 75%). ¹ H-NMR (400 MHz, CDCl ₃ , rt): δ 1.56-1.68 (m, 5H), 2.62 (m, 2H), 3.62 (m, 2H), 6. 87-6.92 (m, 2H), 6.93-6.98 (m, 2H).

The reaction was carried out in the same manner as in Reference Example 1 except that 4- (4-azidophenyl) -1-butanol was used instead of 3- (4-azidophenoxy) -1-propanol. Product was obtained (4.1 g, 0.016 mol, 55%). ¹ H-NMR (400 MHz, CDCl ₃ , rt): δ 1.2-1.85 (m, 4H), 1.94 (s, 3H), 2.62 (m, 2H), 4.14 (M, 2H), 5.57 (t, 1H, J = 1.6 Hz), 6.09-6.12 (br, 1H), 6.85-6.91 (m, 2H), 6.92. -6.97 (m, 2H).

Example 1 [Synthesis of Photoreactive Polymer]
Polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) (5.4 g) and 3- (4-azidophenoxy) propyl methacrylate (0.52 g) produced in Reference Example 1 in a glass Schlenk flask, polymerization started As an agent, 2,2′-azobisisobutyronitrile (AIBN) (15 mg) was weighed. It was diluted with THF to a monomer concentration of 0.8 mol / L and an initiator concentration of 3.75 mmol / L. After sufficiently removing oxygen in the solution with nitrogen, the reaction was carried out at 60 ° C. for 8 hours using a water bath. After completion of the reaction, unreacted monomers were removed by reprecipitation using hexane. By drying under reduced pressure, a brown viscous photoreactive polymer was obtained. The obtained polymer was Mn = 72,000 and Mw / Mn = 3.5. The composition ratio was determined by ¹ H NMR as follows: —OCH ₃ peak derived from PEGMA (3.36-3.40, br, 3H) and aromatic ring peak derived from 3- (4-azidophenoxy) propyl methacrylate (6. 86-6.71, br, 4H). In the following structural formula (7), the value of m / (m + n) was 0.09.

  Structural formula of photoreactive polymer (7)

（ｒは、前記と同じ意味を表す。）
実施例２ ［疎水性ポリマーフィルム表面への固定化］
４ｃｍ×４ｃｍに切り出したポリフッ化ビニリデン（ＰＶＤＦ）フィルム（ＧＬサイエンス製、スマートバッグ２Ｆ）に、実施例１で合成した光反応性ポリマーの２質量％含有溶液（溶媒：ＴＨＦ）を調製することにより作製した表面改質剤を、２０００ｒｐｍで一分間スピンコートした後、高圧水銀灯（東芝ライテック製Ｈ４００Ｐ）により、２秒間ＵＶ照射（２１ｍＪ／ｃｍ^２）を行った。その後、ＴＨＦを用いて掛け洗いし、表面が改質されたフィルム基材を得た。掛け洗い前後でのフィルム表面におけるエステルカルボニルピークの相対強度を比較し、光反応性ポリマーの固定化率を算出したところ、９５％であった。

(R represents the same meaning as described above.)
Example 2 [Immobilization on the surface of a hydrophobic polymer film]
By preparing a solution containing 2% by mass of the photoreactive polymer synthesized in Example 1 (solvent: THF) on a polyvinylidene fluoride (PVDF) film cut out to 4 cm × 4 cm (manufactured by GL Science, Smart Bag 2F). The prepared surface modifier was spin-coated at 2000 rpm for 1 minute, and then subjected to UV irradiation (21 mJ / cm ² ) for 2 seconds using a high-pressure mercury lamp (H400P manufactured by Toshiba Lighting & Technology Corp.). Thereafter, it was washed with THF to obtain a film base having a modified surface. The relative intensity of the ester carbonyl peak on the film surface before and after washing was compared, and the immobilization rate of the photoreactive polymer was calculated to be 95%.

Example 3 [Evaluation of surface hydrophilicity (wetability) by measuring contact angle in water]
The contact angle of the film base material on which the photoreactive polymer prepared in Example 2 was immobilized was about 43 °, and the hydrophilicity was high. This was considered to originate from the hydrophilicity of the PEGMA unit contained in the photoreactive polymer.

Example 4 [Immobilization to PVDF porous membrane]
A PVDF porous membrane (MV020 manufactured by Microdyne Nadia) was immersed in a solution containing 2% by mass of the photoreactive polymer synthesized in Example 1 (solvent: methanol) for 5 minutes, and then at room temperature in a nitrogen atmosphere. And left to dry for 2 hours. Subsequently, UV irradiation (21 mJ / cm ² ) was performed for 2 seconds with a high-pressure mercury lamp (H400P manufactured by Toshiba Lighting & Technology). Then, it wash | cleaned by irradiating an ultrasonic wave for 2 second each in ultrapure water and methanol at room temperature. Thus, a PVDF porous film having a modified surface was obtained.

Example 5 [Confirmation of protein adsorption amount suppression effect]
Insulin (manufactured by Wako Pure Chemical Industries) was used as a sample protein. The surface-modified porous membrane prepared in Example 4 was cut into 1 cm × 1 cm. In an insulin solution (0.1 mg / mL, diluted with PBS, 5 mL), the mixture was shaken (80 rpm) at room temperature for 2 hours, and then washed with PBS. A sample was placed in a φ12 × 105 test tube, 1 mL of Thermo Scientific BCA reagent and 1 mL of 4 wt% PBS solution of sodium dodecyl sulfate were added, and heated at 60 ° C. for 1 hour. Thereafter, the amount of insulin adsorbed on the membrane was quantified by measuring the absorbance of the extract at a wavelength of 562 nm using a spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd., UH5300), and was 0.6 μg / cm ^2. It was. It was shown that the protein adsorption inhibiting ability of the PEGMA unit is functioning effectively on the surface of the surface-modified porous membrane.

Example 6 [Immobilization to polyethylene]
The surface of the film was modified in the same manner as in Example 2 except that the polyvinylidene fluoride (PVDF) film was changed to polyethylene (manufactured by Tosoh Corp., formed from petrocene into a film shape). The immobilization rate was 92%.

Example 7 [Evaluation of hydrophilicity (wetability) of surface by measuring contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 6 was used, the contact angle with water was 46 °.

Example 8 [Immobilization to a porous membrane]
A polyethylene porous membrane whose surface was modified was obtained in the same manner as in Example 4 except that the PVDF porous membrane was changed to a polyethylene porous membrane.

Example 9 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 6 except that the polyethylene porous membrane whose surface was modified in Example 8 was used, and it was 0.8 μg / cm ² .

Example 10 [Immobilization on the surface of a hydrophobic polymer substrate]
The surface of the film was modified in the same manner as in Example 2 except that the polyvinylidene fluoride (PVDF) film was changed to a polyamide film (Mittron, manufactured by Toray Industries, Inc.). The immobilization rate of the photoreactive polymer was 90%. was.

Example 11 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 4 except that the film whose surface was modified in Example 10 was used, the contact angle with water was 54 °.

Example 12 [Immobilization to a porous membrane]
A polyamide porous membrane having a modified surface was obtained in the same manner as in Example 4 except that the PVDF porous membrane was changed to a polyamide porous membrane.

Example 13 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 6 except that the polyamide porous membrane prepared in Example 12 was used, and it was 1.0 μg / cm ² .

Example 14 [Immobilization on the surface of a hydrophobic polymer substrate]
The film was surface-modified in the same manner as in Example 2 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 5 seconds (52.5 mJ / cm ² ). The immobilization rate of the polymer was 100%.

Example 15 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 4 except that the film whose surface was modified in Example 14 was used, the contact angle with water was 43 °.

Example 16 [Immobilization to porous membrane]
A PVDF porous membrane whose surface was modified by the same operation as in Example 4 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 5 seconds (52.5 mJ / cm ² ). Obtained.

Example 17 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 16 was used, and it was 0.4 μg / cm ² .

Example 18 [Immobilization on the surface of a hydrophobic polymer substrate]
The film was surface modified in the same manner as in Example 2 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 30 seconds (315 mJ / cm ² ). The immobilization rate was 100%.

Example 19 [Evaluation of hydrophilicity (wetting) of a surface by measuring a contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 18 was used, the contact angle with water was 42 °.

Example 20 [Immobilization to porous membrane]
A PVDF porous film having a modified surface was obtained by the same operation as in Example 4 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 30 seconds (315 mJ / cm ² ).

Example 21 [Confirmation of protein adsorption suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 20 was used, and it was 0.4 μg / cm ² .

Example 22 Synthesis of photoreactive polymer
A photoreactive polymer was synthesized in the same manner as in Example 1 except that the weight of AIBN used was changed from 15 mg to 30 mg. The obtained polymer was Mn = 33,000, Mw / Mn = 2.1, and the value of m / (m + n) was 0.09.

Example 23 [Immobilization to hydrophobic polymer substrate surface]
Except for using the photoreactive polymer synthesized in Example 23, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 92%.

Example 24 [Evaluation of hydrophilicity (wetting) of a surface by measuring a contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 23 was used, the contact angle with water was 40 °.

Example 25 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 22 was used.

Example 26 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 25 was used, and it was 0.8 μg / cm ² .

Example 27 Synthesis of photoreactive polymer
A photoreactive polymer was synthesized in the same manner as in Example 1 except that the number average molecular weight of polyethylene glycol methyl ether methacrylate was changed from 300 to 950. The obtained polymer was Mn = 93,000, Mw / Mn = 3.0, and the value of m / (m + n) was 0.09.

Example 28 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 27, surface modification was performed on the film in the same manner as in Example 2, and the immobilization rate of the photoreactive polymer was 95%.

Example 29 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 28 was used, the contact angle with water was 45 °.

Example 30 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 27 was used.

Example 31 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 30 was used, and it was 0.5 μg / cm ² .

Example 32 [Synthesis of Photoreactive Polymer]
Except that the weight of polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) used was changed from 5.4 g to 4.2 g, and the weight of the photoreactive monomer was changed from 0.52 g to 0.16 g. The photoreactive polymer was synthesized in the same manner as in 1. The obtained polymer was Mn = 44,000, Mw / Mn = 2.6, and the value of m / (m + n) was 0.3.

Example 33 [Immobilization to hydrophobic polymer substrate surface]
Except for using the photoreactive polymer synthesized in Example 32, surface modification was performed on the film in the same manner as in Example 2, and the immobilization rate of the photoreactive polymer was 97%.

Example 34 [Evaluation of hydrophilicity (wetting) of a surface by measuring a contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 33 was used, the contact angle with water was 45 °.

Example 35 [Immobilization to porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 32 was used.

Example 36 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 5 except that the PVDF porous membrane on which the photoreactive polymer prepared in Example 34 was immobilized was measured and found to be 15 μg / cm ² .

Example 37 [Synthesis of Photoreactive Polymer]
Example except that the weight of polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) used was changed from 5.4 g to 3.0 g and the weight of the photoreactive monomer was changed from 0.52 g to 2.6 g. The photoreactive polymer was synthesized in the same manner as in 1. The obtained polymer had Mn = 30,000, Mw / Mn = 3.0, and the value of m / (m + n) was 0.5.

Example 38 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 37, surface modification was performed on the film in the same manner as in Example 2, and the immobilization rate of the photoreactive polymer was 98%.

Example 39 [Evaluation of hydrophilicity (wetting) of a surface by measuring a contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 38 was used, the contact angle with water was 47 °.

Example 40 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 37 was used.

Example 41 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 5 except that the PVDF porous membrane on which the photoreactive polymer prepared in Example 40 was immobilized was measured and found to be 22 μg / cm ² .

Example 42 [Synthesis of Photoreactive Polymer]
Except that the weight of polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) used was changed from 5.4 g to 5.94 g and the weight of the photoreactive monomer was changed from 0.52 g to 0.052 g. The photoreactive polymer was synthesized in the same manner as in 1. The obtained polymer was Mn = 70,000, Mw / Mn = 2.7, and the value of m / (m + n) was 0.01.

Example 43 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 42, surface modification was performed on the film in the same manner as in Example 2, and the immobilization rate of the photoreactive polymer was 20%.

Example 44 [Evaluation of hydrophilicity (wetting) of a surface by measuring a contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 43 was used, the contact angle with water was 62 °.

Example 45 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 42 was used.

Example 46 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 5 except that the PVDF porous membrane on which the photoreactive polymer prepared in Example 45 was immobilized was measured and found to be 45 μg / cm ² .

Example 47 [Synthesis of Photoreactive Polymer]
Except that the weight of polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) used was changed from 5.4 g to 0.6 g and the weight of the photoreactive monomer was changed from 0.52 g to 4.7 g. The photoreactive polymer was synthesized in the same manner as in 1. The obtained polymer had Mn = 68,000, Mw / Mn = 3.7, and the value of m / (m + n) was 0.9.

Example 48 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 47, surface modification was performed on the film in the same manner as in Example 2, and the immobilization rate of the photoreactive polymer was 100%.

Example 49 [Evaluation of hydrophilicity (wetability) of surface by measuring contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 48 was used, the contact angle with water was 58 °.

Example 50 [Immobilization to a porous membrane]
Except for using the photoreactive polymer synthesized in Example 47, a PVDF porous membrane having a modified surface was obtained by the same operation as in Example 4.

Example 51 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 50 was used, and it was 55 μg / cm ² .

Example 52 [Synthesis of Photoreactive Polymer]
In a glass Schlenk flask, polyethylene glycol methyl ether methacrylate (PEGMA, number average molecular weight = 300) (5.4 g) and 3- (4-azidophenoxy) propyl methacrylate (0.52 g) produced in Reference Example 1, odor Copper (I) chloride (14.4 mg), copper (II) bromide (5.7 mg), and 2,2′-bipyridine (39.1 mg) were weighed. After diluting with 3 mL of acetone and thoroughly removing oxygen in the solution with nitrogen, the temperature was raised to 50 degrees using a water bath, and then ethyl 2-butylisobutyrate (19.5 mg) was added as a polymerization initiator. The reaction was carried out at 50 degrees for 6 hours. After completion of the reaction, unreacted monomers were removed by reprecipitation using hexane. By drying under reduced pressure, a brown viscous photoreactive polymer was obtained. The obtained polymer had Mn = 33,000 and Mw / Mn = 1.6, and the composition ratio had a value of m / (m + n) of 0.07.

Example 53 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 52, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 96%.

Example 54 [Evaluation of hydrophilicity (wetability) of surface by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 53 was used, the contact angle with water was 44 °.

Example 55 [Immobilization to a porous membrane]
Except for using the photoreactive polymer synthesized in Example 52, a PVDF porous membrane having a modified surface was obtained by the same operation as in Example 4.

Example 56 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 55 was used, and it was 0.4 μg / cm ² .

Example 57 [Synthesis of photoreactive polymer]
The 3- (4-azido-2,3,5,6-tetrafluorophenoxy) propyl methacrylate produced in Reference Example 2 was used in place of the 3- (4-azidophenoxy) propyl methacrylate produced in Reference Example 1. In the same manner as in Example 1, a photoreactive polymer represented by the following structural formula (7) was synthesized. The obtained polymer was Mn = 109,000 and Mw / Mn = 5.2. The compositional ratio was determined by ¹ H NMR, PEGMA-derived -OCH ₃ peak (3.36-3.40, br, 3H) and 3- (4-azido-2,3,5,6-tetrafluorophenoxy). ) Determined by the integral ratio of methylene peaks derived from propyl methacrylate (2.00-2.17, br, 2H), and the value of m / (m + n) in the following structural formula (8) was 0.05.

  Structural formula of photoreactive polymer (8)

（ｒは、前記と同じ意味を表す。）
実施例５８ ［疎水性ポリマー基材表面への固定化］
実施例５７で合成した光反応性ポリマーを用いた以外は、実施例２と同様にしてフィルムへの表面改質を行ったところ、光反応性ポリマーの固定化率は９２％だった。

(R represents the same meaning as described above.)
Example 58 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 57, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 92%.

Example 59 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 58 was used, the contact angle with water was 47 °.

Example 60 [Immobilization to a porous membrane]
Except for using the photoreactive polymer synthesized in Example 57, a PVDF porous membrane having a modified surface was obtained by the same operation as in Example 4.

Example 61 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 60 was used, and it was 0.4 μg / cm ² .

Example 62 Synthesis of photoreactive polymer
The following structural formula was obtained in the same manner as in Example 1 except that 4- (4-azidophenyl) butyl methacrylate produced in Reference Example 3 was used instead of 3- (4-azidophenoxy) propyl methacrylate produced in Reference Example 1. The photoreactive polymer shown in (8) was synthesized. The obtained polymer was Mn = 61,000 and Mw / Mn = 2.5. The composition ratio was determined by ¹ H NMR as follows: —OCH ₃ peak derived from PEGMA (3.36-3.40, br, 3H) and aromatic ring peak derived from 4- (4-azidophenyl) butyl methacrylate (6. 86-6.71, br, 4H). In the following structural formula (8), the value of m / (m + n) was 0.09.

  Structural formula of photoreactive polymer (9)

（ｒは、前記と同じ意味を表す。）
実施例６３ ［疎水性ポリマー基材表面への固定化］
実施例６２で合成した光反応性ポリマーを用いた以外は、実施例２と同様にしてフィルムへの表面改質を行ったところ、光反応性ポリマーの固定化率は９４％だった。

(R represents the same meaning as described above.)
Example 63 [Immobilization to hydrophobic polymer substrate surface]
Except for using the photoreactive polymer synthesized in Example 62, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 94%.

Example 64 [Evaluation of surface hydrophilicity (wetting) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 63 was used, the contact angle with water was 44 °.

Example 65 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 62 was used.

Example 66 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 65 was used, and it was 0.4 μg / cm ² .

Example 67 [Synthesis of Photoreactive Polymer]
A photoreactive polymer represented by the following structural formula (9) was obtained in the same manner as in Example 1 except that 2-methacryloyloxyethyl phosphorylcholine (MPC) was used instead of polyethylene glycol methyl ether methacrylate (number average molecular weight = 300). Synthesized. The obtained polymer was Mn = 44,000 and Mw / Mn = 2.6. The composition ratio is ¹ H NMR, MPC-derived —N (CH ₃ ) ₃ peak (3.20-3.45, br, 9H) and 3- (4-azidophenoxy) propyl methacrylate-derived aromatic ring It was determined by the integration ratio of the peak (6.86-6.71, br, 4H). In the following structural formula (9), the value of m / (m + n) was 0.08.

  Structural formula of photoreactive polymer (10)

実施例６８ ［疎水性ポリマー基材表面への固定化］
実施例６７で合成した光反応性ポリマーを用いた以外は、実施例２と同様にしてフィルムへの表面改質を行ったところ、光反応性ポリマーの固定化率は９５％だった。

Example 68 [Immobilization to Hydrophobic Polymer Substrate Surface]
Except for using the photoreactive polymer synthesized in Example 67, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 95%.

Example 69 [Evaluation of hydrophilicity (wetability) of surface by measuring contact angle in water]
The contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Example 68 was used. The contact angle with water was 32 °.

Example 70 [Immobilization to porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 67 was used.

Example 71 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 70 was used, and it was 0.4 μg / cm ² .

Example 72 Synthesis of photoreactive polymer
The photoreactive polymer was synthesized in the same manner as in Example 1 except that the number average molecular weight of polyethylene glycol methyl ether methacrylate was changed from 300 to 4000, the charged amount was 72 g, and the polymerization time was 24 hours. The obtained polymer was Mn = 11,000, Mw / Mn = 1.3, and the value of m / (m + n) was 0.10.

Example 73 [Immobilization on the surface of a hydrophobic polymer substrate]
Except for using the photoreactive polymer synthesized in Example 72, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 93%.

Example 74 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the surface-modified film prepared in Example 73 was used, the contact angle with water was 42 °.

Example 75 [Immobilization to a porous membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Example 72 was used.

Example 76 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Example 75 was used, and it was 0.4 μg / cm ² .

Comparative Example 1 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that an untreated PVDF film was used, the contact angle with water was 82 °.

Comparative Example 2 [Confirmation of protein adsorption amount suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that an untreated PVDF porous membrane was used, and it was 63 μg / cm ² .

Comparative Example 3 [Synthesis of Photoreactive Polymer]
A photoreactive polymer represented by the following structural formula (9) was synthesized in the same manner as in Example 1 except that 3- (4-azidophenylcarboxy) ethyl methacrylate was used instead of 3- (4-azidophenoxy) propyl methacrylate. did. The obtained polymer was Mn = 72,000 and Mw / Mn = 3.5. The composition ratio was determined by ¹ H NMR as follows: —OCH ₃ peak derived from PEGMA (3.36-3.40, br, 3H) and aromatic ring peak derived from 3- (4-azidophenylcarboxy) ethyl methacrylate (8 .00-8.11, 7.09-7.17, br, 2H). In the following structural formula (10), the value of m / (m + n) was 0.09. Structural formula of photoreactive polymer (11)

（ｒは、前記と同じ意味を表す。）
比較例４ ［疎水性ポリマー基材表面への固定化］
比較例３で合成した光反応性ポリマーを用いた以外は、実施例３と同様にしてフィルムへの表面改質を行ったところ、光反応性ポリマーの固定化率は１１％だった。

(R represents the same meaning as described above.)
Comparative Example 4 [Immobilization to Hydrophobic Polymer Substrate Surface]
Except that the photoreactive polymer synthesized in Comparative Example 3 was used, surface modification was performed on the film in the same manner as in Example 3. As a result, the immobilization rate of the photoreactive polymer was 11%.

Comparative Example 5 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Comparative Example 3 was used, the contact angle with water was 62 °.

Comparative Example 6 [Immobilization to Porous Membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Comparative Example 3 was used.

Comparative Example 7 [Confirmation of protein adsorption suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Comparative Example 6 was used, and it was 47 μg / cm ² .

Comparative Example 8 [Immobilization to Hydrophobic Polymer Substrate Surface]
The film was surface-modified in the same manner as in Comparative Example 4 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 5 seconds (52.5 mJ / cm ² ). The immobilization rate of the functional polymer was 23%.

Comparative Example 9 [Evaluation of hydrophilicity (wetting) of the surface by measuring the contact angle in water]
When the contact angle was measured in the same manner as in Comparative Example 5 except that the film whose surface was modified in Comparative Example 8 was used, the contact angle with water was 59 °.

Comparative Example 10 [Immobilization to Porous Membrane]
A PVDF porous membrane whose surface was modified by the same operation as in Comparative Example 6 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 5 seconds (52.5 mJ / cm ² ). Got.

Comparative Example 11 [Confirmation of protein adsorption amount suppression effect]
The amount of adsorbed insulin was measured by the same operation as in Comparative Example 7 except that the PVDF porous membrane prepared in Comparative Example 10 was used, and it was 38 μg / cm ² .

Comparative Example 12 [Immobilization to Hydrophobic Polymer Substrate Surface]
Except for changing the UV irradiation time from 2 seconds (21 mJ / cm ² ) to 30 seconds (315 mJ / cm ² ), the photoreactive polymer was immobilized on the film in the same manner as in Comparative Example 4, The immobilization rate was 42%.

Comparative Example 13 [Evaluation of hydrophilicity (wetting) of the surface by measuring the contact angle in water]
When the contact angle was measured in the same manner as in Comparative Example 5 except that the film whose surface was modified in Comparative Example 12 was used, the contact angle with water was 57 °.

Comparative Example 14 [Immobilization to Porous Membrane]
A PVDF porous membrane having a modified surface was obtained by the same operation as in Comparative Example 6 except that the UV irradiation time was changed from 2 seconds (21 mJ / cm ² ) to 30 seconds (315 mJ / cm ² ). It was.

Comparative Example 15 [Confirmation of protein adsorption suppression effect]
The amount of insulin adsorbed was measured by the same operation as in Comparative Example 7 except that the PVDF porous membrane prepared in Comparative Example 14 was used, and it was 29 μg / cm ² .

Comparative Example 16 [Synthesis of Photoreactive Polymer]
Instead of 3- (4-azidophenoxy) propyl methacrylate, 2- (4-azidophenoxy) ethyl methacrylate (in Reference Example 1, 2-bromo-1-ethanol was used instead of 3-bromo-1-propanol, and A photoreactive polymer represented by the following structural formula (12) was synthesized in the same manner as in Example 1 except that the production method was used. The obtained polymer was Mn = 60,000 and Mw / Mn = 2.7. The composition ratio was determined by ¹ H NMR as follows: —OCH ₃ peak derived from PEGMA (3.36-3.40, br, 3H) and aromatic ring peak derived from 2- (4-azidophenoxy) ethyl methacrylate (6. 86-6.71, br, 4H), and the m / (m + n) value was 0.08.

  Structural formula of photoreactive polymer (12)

比較例１７ ［疎水性ポリマーフィルム表面への固定化］
比較例１６で合成した光反応性ポリマーを用いた以外は、実施例２と同様にしてフィルムへの表面改質を行ったところ、光反応性ポリマーの固定化率は５５％だった。

Comparative Example 17 [Immobilization to Hydrophobic Polymer Film Surface]
Except that the photoreactive polymer synthesized in Comparative Example 16 was used, surface modification was performed on the film in the same manner as in Example 2. As a result, the immobilization rate of the photoreactive polymer was 55%.

Comparative Example 18 [Evaluation of surface hydrophilicity (wetability) by measurement of contact angle in water]
When the contact angle was measured in the same manner as in Example 3 except that the film whose surface was modified in Comparative Example 17 was used, the contact angle with water was 57 °.

Comparative Example 19 [Immobilization to Porous Membrane]
A PVDF porous membrane with a modified surface was obtained in the same manner as in Example 4 except that the photoreactive polymer synthesized in Comparative Example 16 was used.

Comparative Example 20 [Measurement of protein adsorption amount]
The amount of insulin adsorbed was measured by the same operation as in Example 5 except that the PVDF porous membrane prepared in Comparative Example 19 was used, and it was 27 μg / cm ² .

Claims (4)

A photoreactive polymer having a structure represented by the following general formula (1) and having a number average molecular weight of 1,000 to 1,000,000.

(In the formula, m and n each independently represent an integer of 1 or more, X represents a phenylene group which may have a substituent, or a group represented by an ester bond or an amide bond, and Y represents a betaine property. Represents a hydrophilic group selected from a group, an alkoxyalkyl group, an alkoxypolyoxyethylene group, and a hydroxypolyoxyethylene group, Z represents a group represented by —O— or —N (R ₃ ) —, and A represents — Represents a group represented by O— or —CH ₂ —, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a C _{1 to} C ₆ hydrocarbon group, and R ₄ represents C _{3 to} C _6. And R ₅ represents a fluorine atom, and p represents an integer of 0 to 4.) The photoreactive polymer of Claim 1 which has a structure shown by following General formula (2).

(In the formula, m, n, Z, A, R ₁ , R ₂ , R ₄ , R ₅ and p represent the same meaning as described above. The value of r represents an integer of 2 to 90.) The photoreactive polymer of Claim 1 which has a structure shown by following General formula (3).

(In the formula, m and n each independently represent an integer of 1 or more, r represents an integer of 2 to 90, and R ₄ represents a C _{3 to} C ₆ divalent hydrocarbon group.) The photoreactive polymer according to any one of claims 1 to 3, wherein a value of m / (m + n) is 0.02 to 0.7.