JP2009046529A - Fluororesin molded body having hydrophilic polymer on surface and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of producing a surface-hydrophilized fluororesin molded body which substantially avoids a change in the internal properties of the molded body and adsorbs a small amount of protein. <P>SOLUTION: The method for producing a fluororesin molded body having a hydrophilic polymer on a surface thereof includes a step (A) of bonding a polymerization initiator compound to a surface of a fluororesin molded body, and a step (B) of polymerizing a hydrophilic monomer with the polymerization initiator compound as a starting point. The step (A) is preferably carried out by subjecting the surface of the fluororesin molded body to UV treatment to introduce a hydrophilic group into the surface, and reacting the hydrophilic group with the polymerization initiator compound. The step (B) is preferably carried out by atom transfer radical polymerization. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fluororesin molded article having a hydrophilic surface suitable for biomaterials, in which adsorption of biological substances such as proteins is suppressed, and a method for producing the same.

  Biomaterials, which are materials that are used by being brought into direct contact with a living body, may have their functions impaired due to adsorption of biological substances such as proteins on the surface. Therefore, biomaterials are required to suppress adsorption of proteins and the like. For example, in a medical device such as an artificial blood vessel or an artificial heart-lung machine, protein adsorption may start and a thrombus may occur. If the blood flow is blocked by thrombus formation, a serious crisis will be caused, so the use range and expiration date of the biomaterial may be limited. Further, in contact lenses and the like, dirt adheres due to adsorption of proteins and lipids, and the expiration date is limited.

  On the other hand, fluororesins, particularly polytetrafluoroethylene (PTFE), are preferred as biomaterials because of their high chemical resistance and stability. However, since the hydrophobicity is very high, there is a problem that it is easy to adsorb proteins and the like due to hydrophobic interaction, and the usage form is limited in applications where the adsorption of biological substances such as proteins is a problem. . For example, in an artificial blood vessel made of porous PTFE, those having a diameter of 5 mm or less cannot be used for a long time because of thrombus formation.

  Examples of means for suppressing the adsorption of biological substances such as proteins include hydrophilizing the surface of the biomaterial to reduce the hydrophobic interaction with the protein. As a method for hydrophilizing the surface of the fluororesin, specifically, for example, by the method described in Patent Document 1, the PTFE film is irradiated with radiation at a temperature equal to or higher than the crystal melting point in the absence of oxygen to crosslink PTFE. After improving the strength, there is a method in which, for example, a method described in Patent Document 2 is used to fill a PTFE film with a monomer solution and irradiate with radiation to polymerize. According to this method, a fluororesin molded product having a hydrophilic polymer on the surface can be produced. However, in this method, not only the film surface but also the inside of the film is modified. Therefore, the inherent properties of PTFE such as chemical resistance, strength and stability may be impaired inside the PTFE, which is suitable for biomaterial applications. Absent.

On the other hand, corona discharge, UV treatment, and plasma treatment are treatments having lower energy than radiation treatment, and in general, only the surface can be modified. However, in PTFE, since fluorine atoms recombine, these treatments usually cannot be hydrophilized. On the other hand, in Patent Document 3, there is a method of hydrophilizing the surface by irradiating a fluororesin with an excimer laser in the presence of a compound having an atom having a bond energy with a fluorine atom of 128 kcal / mol or more and a hydrophilic group. Are listed. In this method, recombination of fluorine atoms is prevented and hydrophilization is facilitated. However, the fluororesin having a hydrophilic surface obtained by this method is still insufficient although the degree of protein adsorption is reduced.
JP-A-6-116423 JP 2005-63778 A Japanese Unexamined Patent Publication No. Hei 6-2933837

  An object of the present invention is to provide a method capable of producing a fluororesin molded body having a surface modified to be hydrophilic and having a small amount of protein adsorption, a small amount of protein adsorption, and the like. Another object of the present invention is to provide a fluororesin molded body having a small amount of protein adsorbed and having a hydrophilic surface modified.

The present invention includes a step (A) of bonding a polymerization initiator compound to the surface of a fluororesin molded body, and a step (B) of polymerizing a hydrophilic monomer starting from the polymerization initiator compound.
And a method for producing a fluororesin molded body having a hydrophilic polymer on the surface.

Further, the present invention is a fluororesin molded body having a hydrophilic polymer covalently bonded to the surface,
The said hydrophilic polymer is a fluororesin molded object which is poly (meth) acrylic acid ester which has a hydrophilic group in a side chain.

  According to the production method of the present invention, since a method by UV irradiation can be used, there is a possibility that the inside of the fluororesin molded body may be unnecessarily modified like the conventional method of initiating polymerization of a hydrophilic polymer by irradiation with radiation. Low. Moreover, since hydrophilicity is imparted by bonding a hydrophilic polymer to the fluororesin molded body, many hydrophilic groups can be introduced into the fluororesin molded body, and the degree of hydrophilization can be easily improved. Can do. Furthermore, not only the effect of hydrophilizing the surface of the fluororesin molded body but also the excluded volume effect due to the movement of the hydrophilic polymer can suppress the adsorption of biological substances such as proteins to the surface of the fluororesin molded body. Therefore, it is possible to obtain a fluororesin molded body in which the property inside the molded body is small, the amount of protein adsorption is small, and the surface is modified to be hydrophilic. The fluororesin molding in which the surface of the present invention is modified to be hydrophilic is suitable for biomaterial applications.

  First, the manufacturing method of this invention is demonstrated.

  The fluororesin constituting the molded article used in the present invention is not particularly limited, but perfluororesin is preferable from the viewpoint of chemical stability, in-vivo stability, and cleanliness. For example, polytetrafluoroethylene (PTFE) ), Tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and the like. Among them, PTFE is most preferable because it is used as a prosthetic material in vivo such as an artificial blood vessel, an artificial dura mater, and an artificial pericardium.

  The shape of the molded body may be appropriately selected according to the use such as a film, a sheet, or a plate, and the molded body may be a porous body.

  Regarding the polymerization initiator compound, in the present invention, polymerization initiator compounds for various polymerization methods such as radical polymerization, anionic polymerization, and cationic polymerization can be appropriately selected and used according to the kind of the hydrophilic monomer to be used. In the present invention, from the viewpoint that the operation is simple and suitable for mass production, the polymerization in the step (B) is preferably performed by radical polymerization, and among them, the ease of bonding to the surface of the fluororesin molded body, the polymerization initiator, and the like. From the viewpoint of the stability of the compound and the ease of molecular design of the hydrophilic polymer, it is particularly preferred to carry out by atom transfer radical polymerization (ATRP). Accordingly, the polymerization initiator compound is preferably a radical polymerization initiator compound, and more preferably an atom transfer radical polymerization initiator compound. Examples of the initiator compound for atom transfer radical polymerization include monofunctional, difunctional or polyfunctional organic halides or sulfonyl halide compounds.

  Moreover, what has a functional group which can couple | bond with a fluororesin molded object is used for a polymerization initiator compound. Here, the functional group that can be bonded to the fluororesin molded body reacts with a radical generated on the surface of the fluororesin molded body by irradiation of energy rays or a functional group introduced on the surface to bond with the fluororesin molded body. It is a functional group that can be used.

  The hydrophilic monomer used in the present invention is polymerized on the surface of the fluororesin molded body by the above polymerization initiator compound and grafted to the fluororesin molded body. Accordingly, the type of hydrophilic monomer, particularly the type of hydrophilic group possessed by the hydrophilic monomer and the type of polymerizable functional group may be appropriately selected according to the use of the final product. In the case of applying a fluororesin molded body having a hydrophilic polymer on the surface for biomaterial use, the hydrophilic group of the monomer is a nonionic hydrophilic group such as ether or alcohol from the viewpoint of biocompatibility and excluded volume effect. It is preferable that Examples of such nonionic hydrophilic groups include polyoxyalkylene groups such as polyoxyethylene groups and polyoxypropylene groups; monosaccharides such as glucose, fructose and mannose; disaccharides such as lactose; and saccharide compounds such as oligosaccharides. Examples include residues. Here, the residue of the saccharide compound refers to a group having a structure formed by removing one or more hydrogen atoms from the saccharide compound. The polyoxyalkylene group may be one in which oxyalkylene units are repeatedly bonded with a degree of polymerization of about an oligomer. The hydrophilic group may be protected by a protecting group. The hydrophilic monomer is preferably a (meth) acrylic acid ester having a hydrophilic group in the ester side chain. Therefore, the hydrophilic monomer is more preferably a (meth) acrylic acid ester having a polyoxyalkylene group or a saccharide compound residue in the side chain.

  In the step (A), a polymerization initiator compound is bonded to the surface of the fluororesin molded body. As a method for this, for example, there is a method in which a radical is generated by irradiating the surface of a fluororesin molded body with radiation, corona discharge, UV irradiation or plasma irradiation to react the polymerization initiator compound with the radical. However, the method of irradiating with radiation is not preferable in the method of the present invention because the energy is too high and the inside of the fluororesin molded body may be modified and the characteristics may be changed. In order to prevent a change in the properties inside the molded body, the present invention recommends that the step (A) is performed by a method of performing corona discharge, UV irradiation, or plasma irradiation.

  In order to perform the step (A) by the UV treatment, specifically, for example, the step (A-1) of introducing a hydrophilic group into the surface by subjecting the surface of the fluororesin molded body to UV treatment, and the hydrophilic group. It is preferable to perform the process (A-2) which makes a polymerization initiator compound react.

  Usually, when the surface of the fluororesin molded body is subjected to UV treatment, it usually occurs that the fluorine atoms detached from the fluororesin recombine with the fluororesin. In order to prevent this, in the step (A-1), for example, as in the method described in Patent Document 3, a compound having an atom having a bond energy with a fluorine atom of 128 kcal / mol or more and a hydrophilic group (hereinafter, referred to as the method described in Patent Document 3). In the presence of a fluorine-trapping compound, a hydrophilic group is introduced onto the surface of the fluororesin molding by irradiating the fluororesin molding with UV.

  As the fluorine scavenging compound, aluminum hydroxide, boric acid, ammonium borate, lithium hydroxide, calcium hydroxide, barium hydroxide and the like can be used. These are preferably used in the form of an aqueous solution. Moreover, in order to raise the solubility of a solute, you may add alkali salts, such as sodium hydroxide and potassium hydroxide.

  As a specific operation, for example, as shown in FIG. 1, an aqueous solution 2 of a fluorine-trapping compound is applied on a sample table 1 and a fluororesin film 3 is placed thereon. Then, the fluororesin film 3 is irradiated with UV from the low-pressure mercury lamp 4. This UV irradiation causes hydrophilization on the surface of the fluororesin film 3 in contact with the aqueous solution 2. For example, when the aqueous solution 2 is a hydroxide aqueous solution, hydroxyl groups are introduced into the surface of the fluororesin film 3.

  As another example, as shown in FIG. 2, a fluororesin film 3 ′ is placed on a sample table 1 ′, and an aqueous solution 2 ′ of a fluorine scavenging compound is applied. Further, quartz glass 5 'is placed thereon, and the aqueous solution 2' is sandwiched between the quartz glass 5 'and the fluororesin film 3'. Then, the fluororesin film 3 ′ is irradiated with UV from the low pressure mercury lamp 4 ′ through the quartz glass 5 ′. By this UV irradiation, hydrophilic groups are introduced into the surface of the fluororesin film 3 ′ that is in contact with the aqueous solution 2 ′ of the fluorine scavenging compound, thereby causing hydrophilicity.

  As described above, hydrophilic groups such as hydroxyl groups are introduced on the surface of the fluororesin molded body.

  In the step (A-2), a polymerization initiator compound having a functional group capable of binding to the fluororesin by reacting with the hydrophilic group introduced on the surface of the fluororesin molded body is used. For example, when a hydroxide is used as the fluorine scavenging compound and a hydroxyl group is introduced on the surface of the fluororesin molded body, a carboxyl group, an acid halide group (—COX) can be used as a functional group capable of binding to the fluororesin. X is halogen), an epoxy group, or the like may be selected. In view of easy availability of various compounds, it is preferable to select a carboxyl group or an acid halide group. In the step (A-2), such a polymerization initiator compound may be reacted with a hydrophilic group introduced on the surface of the fluororesin molded body, and the reaction conditions are the introduced hydrophilic group and the above functional group. The general conditions for the reaction with can be used. For example, when the hydrophilic group introduced into the fluororesin is a hydroxyl group and the polymerization initiator has a carboxyl group or an acid halide group, the general reaction conditions for the esterification reaction between these functional groups are adopted. Good. However, it is important to select reaction conditions that do not impair the polymerization initiating ability of the polymerization initiator compound.

  Step (B) is a step of polymerizing a hydrophilic monomer starting from the polymerization initiator compound. It can be carried out by any polymerization method such as radical polymerization, cationic polymerization, anionic polymerization, etc., and this step is carried out by appropriately selecting general polymerization conditions according to the kind of the polymerization initiator compound and the hydrophilic monomer. Just do it.

  In the case where the initiator compound of atom transfer radical polymerization is bonded in step (A) and step (B) is performed by atom transfer radical polymerization, for example, K. Matyjaszewski, and J. Xia, “Atom Transfer Radical Polymerization” , Chem. Rev. (2001) 101, p.2921-2990, and M. Kamigaito, T. Ando, and M. Sawamoto, “Metal-Catalyzed Living Radical Polymerization”, Chem. Rev. (2001) 101, p. The step (B) can be performed according to the method described in the literature such as 3689-3745. When the step (B) is performed by atom transfer radical polymerization, a transition metal catalyst or a ligand is used, but those that can be used in ordinary atom transfer radical polymerization can be used. For example, the transition metal included in the transition metal catalyst includes monovalent and zerovalent copper, divalent ruthenium, divalent iron, divalent nickel, and the like. Further, examples of the ligand include polyamines such as 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, and the like. Etc.

  As described above, a fluororesin molded body having a hydrophilic polymer on the surface can be produced. An example of the above process is briefly shown in FIG. 3 using a scheme.

  Step (1) in FIG. 3 corresponds to the above step (A-1), and here, a PTFE film is used as the fluororesin molded body. An aluminum hydroxide / sodium hydroxide aqueous solution is used as the aqueous solution of the fluorine scavenging compound. By irradiating UV as shown in FIG. 1 or FIG. 2, hydroxyl groups are introduced on the surface of the PTFE film.

  Step (2) corresponds to the above step (A-2), and here, 2-bromoisobutyric acid bromide is used as the polymerization initiator compound. By reacting the hydroxyl group on the surface of the PTFE film with the -COBr group of the polymerization initiator compound, the polymerization initiator compound is bonded to the surface of the PTFE film via an ester bond.

  Step (3) corresponds to the step (B). Here, poly (ethylene glycol) methyl ether methacrylate which is a (meth) acrylic acid ester having a polyoxyalkylene group in the side chain is used as the hydrophilic monomer. Moreover, CuBr is used as a transition metal catalyst, and bipyridyl is used as a ligand. By polymerizing the hydrophilic monomer with the movement of Br atoms by the polymerization initiator compound, transition metal catalyst and ligand bonded to the surface of the PTFE film, the hydrophilic polymer is introduced to the surface through a covalent bond. PTFE film is obtained. In FIG. 3, the hydrophilic polymer is a polymacromonomer and a comb polymer.

  According to the production method of the present invention, since a method by UV irradiation can be used, there is a possibility that the inside of the fluororesin molded body may be unnecessarily modified like the conventional method of initiating polymerization of a hydrophilic polymer by irradiation with radiation. Low. Moreover, since hydrophilicity is imparted by bonding a hydrophilic polymer to the fluororesin molded body, many hydrophilic groups can be introduced into the fluororesin molded body, and the degree of hydrophilization can be easily improved. Can do. Furthermore, not only the effect of hydrophilizing the surface of the fluororesin molded body but also the excluded volume effect due to the movement of the hydrophilic polymer can suppress the adsorption of biological substances such as proteins to the surface of the fluororesin molded body. . The polymerization initiator species can be selected, and the hydrophilic monomer can be polymerized by precision polymerization such as atom transfer radical polymerization. According to the precise polymerization, the control of the polymerization is easy, and the range of possible molecular designs of the hydrophilic polymer is wide. Therefore, it is easy to adjust the surface state (hydrophilicity degree, etc.) of the fluororesin molded body.

  The fluororesin molded body having a hydrophilic polymer on the surface obtained by the production method of the present invention has the property that the surface is hydrophilic in addition to the properties unique to the fluororesin. Therefore, the said fluororesin molded object can be applied to the various uses which can utilize these characteristics, and is suitable for a biomaterial use especially. In the present invention, the biomaterial refers to a material that is used by being brought into direct contact with a living body, and examples thereof include prosthetic materials such as artificial blood vessels, artificial dura mater and artificial pericardium, and contact lenses.

  The present invention is also a fluororesin molded product in which a hydrophilic polymer is covalently bonded to the surface, wherein the hydrophilic polymer is a poly (meth) acrylate ester having a hydrophilic group in a side chain. It is. Poly (meth) acrylic acid ester is a polymer with a high degree of freedom in selecting the type and length of the ester group in the side chain, and can have a large number of hydrophilic groups, and the degree of hydrophilicity of the surface of the fluororesin molded product It is also easy to increase.

  When the fluororesin molded product is applied to biomaterials, the hydrophilic group in the side chain of the hydrophilic polymer is a polyoxyethylene group such as polyoxyethylene group or polyoxypropylene group from the viewpoint of biocompatibility and excluded volume effect. It is preferably an alkylene group; a residue of a monosaccharide such as glucose, fructose or mannose, a disaccharide such as lactose, or a saccharide compound such as an oligosaccharide.

  More preferably, the hydrophilic polymer is a comb polymer. The comb polymer refers to a polymer having a number of trident branching points with linear side chains in the main chain. When the hydrophilic polymer is a comb polymer, the amount of hydrophilic groups grafted on the fluororesin molded article can be easily increased by increasing the side chain length, etc. By adjusting the thickness, the excluded volume effect can be enhanced. The comb polymer is preferably a macromonomer polymer or copolymer. The macromonomer refers to a polymer or oligomer having a polymerizable functional group at the terminal, and examples thereof include (meth) acrylic acid ester having a polyoxyalkylene group in the side chain.

  The fluororesin constituting the molded body is not particularly limited, but perfluororesin is preferable from the viewpoint of chemical stability, in-vivo stability, and cleanness. Examples thereof include polytetrafluoroethylene (PTFE) and tetrafluoroethylene. -A hexafluoropropylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), etc. are mentioned. Among them, PTFE is most preferable because it is used as a prosthetic material in vivo such as an artificial blood vessel, an artificial dura mater, and an artificial pericardium. The shape of the molded body may be appropriately selected according to the use such as a film, a sheet, or a plate, and the molded body may be a porous body.

  The hydrophilic polymer is covalently bonded to the fluororesin, but the fluororesin and the hydrophilic polymer are bonded via a polymerization initiator compound fragment as in the fluororesin molded product obtained by the above production method. May be.

  In the present invention, the static contact angle between the surface of the fluororesin molded body and water is preferably 80 ° or less. By making the said contact angle 80 degrees or less, the hydrophobic interaction of protein and a fluororesin molded object can fully be reduced. In addition, the said contact angle becomes so small that the hydrophilicity of the surface of a fluororesin molded object is high. Therefore, in order to reduce the contact angle, it is only necessary to increase the binding amount of the hydrophilic polymer, increase the number of hydrophilic groups of the hydrophilic polymer, or the like.

  The fluororesin molded product of the present invention can be used for biomaterials according to a known method, and the biomaterials can be used for biomaterials such as proteins due to the effect based on the hydrophilicity of the polymer grafted on the surface and the excluded volume effect. Adsorption is extremely suppressed.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to a following example.

Example 1
As a treatment liquid containing a fluorine-trapping compound, an Al (OH) ₃ / NaOH aqueous solution having a concentration of Al (OH) ₃ of 0.1 mol / l and a concentration of NaOH of 5 mol / l is used, and the configuration as shown in FIG. Then, a PTFE film (thickness 0.1 mm, water static contact angle 123 °) was irradiated with UV for 30 minutes with a low-pressure mercury lamp to introduce hydroxyl groups on the surface of the PTFE film. The static contact angle between the treated surface of the PTFE film and water was 62 °. Next, 2-bromoisobutyric acid bromide was bonded to the PTFE surface by esterification with a hydroxyl group on the PTFE film surface as a polymerization initiator compound. I let you.

  Starting from a polymerization initiator compound bonded to the surface of the PTFE film, poly (ethylene glycol) methyl ether methacrylate (PEGMEMA, Mn = 475, polymerization degree of side chain poly (ethylene glycol) = 8) is a hydrophilic monomer, Atom transfer radical polymerization was performed using CuBr as the catalyst, 2,2′-bipyridyl as the ligand, and toluene as the solvent. The initial monomer concentration was 50 wt%, the polymerization temperature was 60 ° C., and the polymerization time was 8 hours. The PTFE film was rinsed, washed, and dried to obtain a PTFE film having a polymer of PEGMEMA on the surface.

Examples 2-4
A PTFE film having a PEGMEMA polymer on its surface was prepared in the same manner as in Example 1 except that the polymerization time was changed.

Examples 5-6
In the same manner as in Example 1, a PTFE film having 2-bromoisobutyric acid bromide bonded to the surface was produced. Subsequently, isopropylidene glucose-supporting methacrylate (MAIpGlc) was used as a hydrophilic monomer, and atom transfer radical polymerization was performed using CuBr as a catalyst, 2,2′-bipyridyl as a ligand, and anisole as a solvent. The initial monomer concentration was 50 wt%, the polymerization temperature was 50 ° C., and the polymerization time was 5 hours (Example 5) and 12 hours (Example 6). The resulting PTFE film was rinsed, washed and dried. Thereafter, the PTFE film was immersed in 90% HCOOH and stirred at room temperature for 40 hours to deprotect the poly MAIpGlc to obtain a PTFE film having polyglucose-supported methacrylate on the surface.

Comparative Example 1
As a treatment liquid containing a fluorine-trapping compound, an Al (OH) ₃ / NaOH aqueous solution having a concentration of Al (OH) ₃ of 0.1 mol / l and a concentration of NaOH of 5 mol / l is used, and the configuration as shown in FIG. Then, the PTFE film (thickness 0.1 mm, water static contact angle 123 °) was irradiated with UV for 30 minutes with a low-pressure mercury lamp. The obtained PTFE film having a hydroxyl group on its surface was used as the film of Comparative Example 1. The static contact angle between the treated surface of this PTFE film and water was 62 °.

  Table 1 summarizes the polymerization time and the contact angle between the obtained film surface and water in each example. Moreover, the result of the number average molecular weight (Mn) obtained from the GPC analysis of the polymer produced | generated in the solution is also shown as a standard of a polymerization degree. Furthermore, about Examples 1-4, the result of the oxygen element ratio calculated | required by XPS measurement is also shown as a standard of the amount of hydrophilic groups.

Protein adsorption experiment Bovine serum albumin (BSA) was used as the protein. The PTFE films of Examples 1 to 6 and Comparative Example 1 and the untreated PTFE film as a blank were immersed in 1 ml of a BSA PBS solution having a concentration of 20 μg / ml for 2 hours. After soaking, it was washed with distilled water and dried. XPS measurement was performed on the obtained sample, and the protein adsorptivity was evaluated from the result of the N element ratio. The results are shown in Table 1.

  As is clear from Table 1, in the PTFE films of all Examples, N element is not detected, and it can be seen that protein adsorption is extremely suppressed.

  The present invention is a method for producing a fluororesin molded body whose surface is modified to be hydrophilic, and the fluororesin molded body obtained by the method has a characteristic that the surface is hydrophilic in addition to the characteristics unique to the fluororesin. Therefore, it can be applied to various uses (especially biomaterials use) in which these characteristics are utilized.

It is a figure which shows an example of UV treatment of the surface of a fluororesin molded object. It is a figure which shows another example of UV treatment of the surface of a fluororesin molded object. It is a scheme which shows the outline of an example of the manufacturing method of this invention.

Explanation of symbols

1,1 'sample stage 2,2' aqueous solution of fluorine scavenging compound 3,3 'fluorine resin film 4,4' low pressure mercury lamp 5 'quartz glass

Claims (10)

A step (A) of bonding a polymerization initiator compound to the surface of the fluororesin molding, and a step (B) of polymerizing a hydrophilic monomer starting from the polymerization initiator compound
The manufacturing method of the fluororesin molding which has a hydrophilic polymer on the surface containing this.   In the step (A), the surface of the fluororesin molded body is treated with UV to introduce a hydrophilic group into the surface (A-1), and the step of reacting the hydrophilic group with a polymerization initiator compound (A -2). The manufacturing method of Claim 1 containing. The polymerization initiator compound in the step (A) is an initiator compound for atom transfer radical polymerization,
The production method according to claim 1 or 2, wherein the polymerization in the step (B) is performed by atom transfer radical polymerization.   The manufacturing method according to any one of claims 1 to 3, wherein the hydrophilic monomer is a (meth) acrylic acid ester having a polyoxyalkylene group or a saccharide compound residue in a side chain. A fluororesin molded body having a hydrophilic polymer covalently bonded to the surface,
A fluororesin molded product, wherein the hydrophilic polymer is a poly (meth) acrylic acid ester having a hydrophilic group in a side chain.   The fluororesin molded product according to claim 5, wherein the hydrophilic group of the side chain is a residue of the polyoxyalkylene group or a saccharide compound.   The fluororesin molded body according to claim 5 or 6, wherein the hydrophilic polymer is a comb polymer.   The fluororesin molded body according to any one of claims 5 to 7, wherein the fluororesin is polytetrafluoroethylene.   The fluororesin molded body according to any one of claims 5 to 8, wherein a static contact angle between the surface and water is 80 ° or less.   The biomaterial using the fluororesin molded object of any one of Claims 5-9.

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