JPH0543634A - Graft polymer - Google Patents

Abstract

PURPOSE:To obtain a graft polymer which is excellent in hydrophilicity and has low frictional properties not accompanied by adsorptivity by grafting a specific polymerizable monomer onto a polymer material. CONSTITUTION:A polymerizable monomer having a sugar residue (e.g. 2- glycosylethyl methacrylate) is grafted onto a polymer material (e.g. a polyether polyurethane film).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel graft polymer. More specifically, it relates to a hydrophilic graft polymer.

[0002]

2. Description of the Related Art Generally, polymer materials are indispensable as materials having many preferable properties such as light weight, strong or supple, and chemically inert, but most of them are It is water repellent. By modifying only the surface layer of this polymer, while maintaining the original desirable properties of the original polymer, it is highly hydrophilic and durable, contrary to water repellency, and easily wets with water or body fluids. Further, if a polymer material having a surface exhibiting low friction property in a wet state can be obtained, it is most suitable as a material for medical equipment / apparatus. Since such polymeric materials cut off water or body fluids easily, they are considered to be easily inserted into the body and less likely to damage mucous membranes.For example, medical devices such as infusion tubes, blood tubes and catheters It is useful as a material for equipment.

Conventionally, as a method of hydrophilizing the surface of such a polymer material, a method of treating the polymer material by low temperature plasma (glow discharge, corona discharge) Graft polymerization of a polymerizable monomer having a hydrophilic group The so-called graft polymerization method, which is a method of applying a coating material comprising a copolymer having a hydrophilic group-containing monomer or a copolymer containing the monomer as a component, has been carried out.

The above methods are very surface-only treatments and are not sufficient to impart low friction to the material.
As an example of the above, for example, Raft et al. [JP-A-59-164709]
No.] obtained by graft-polymerizing acrylamide or N, N-dimethylacrylamide onto a polyurethane removable denture, and obtained an improved denture surface that gives a slimy or slimy feel when moistened with saliva. However, the surface obtained by graft-polymerizing N, N-dimethylacrylamide is limited in application because the functional groups available for the reaction are scarce.

In the above coating method, for example, Nagaoka et al. Reported that the first layer was a polymer layer having an amino group obtained by hydrolyzing an isocyanate group on the surface, and the second layer was bonded to the amino group. It has proposed a coating film consisting of a polymer layer having a possible epoxy group and a pyrrolidone group as a hydrophilic group [Biomaterials (Biomateri
al., Vol. 11, p. 419 (1990)], the film-forming process including the production of these polymers is complicated, and the compatibility with the polymer material as the base material is also a problem.

In the above-mentioned graft polymerization method of the polymerizable monomer, a polymerization initiation point is created on the surface of the polymer, the monomer is polymerized, and the graft chain is grown from there.
To create a polymerization initiation point, plasma irradiation, light (ultraviolet light, visible light (with photosensitizer) irradiation), addition of oxides such as ammonium persulfate, Fe ²⁺ together with peroxide
There is a redox method in which ions are present, a method using an oxidizing agent such as Ce ⁴⁺ , Cr ⁶⁺ or Mn ^7+, and ozone, which is one of the peroxides, is -1 ozone itself. In addition to modification, it is also used to introduce a functional group that serves as a polymerization initiation point in -2 graft polymerization.

As an example of the above-mentioned -2, for example, graft polymerization of polyethylene with vinyl chloride [Takayuki Otsu, Masayoshi Kinoshita, Experimental method of polymer synthesis (Kagaku Dojin 1972) 38
Page 8, << Experimental Example 1433 >>], Graft Polymerization of High Density Polyethylene and Polyurethane with Acrylamide or N, N-Dimethylacrylamide [ ^a) Takebayashi et al., 35th Polymer Research Conference (Kobe) (1989) Proceedings , 9; ^b) Sekine et al., 40th SPSJ Proceedings, 40 (4), 1448
(1991) << II-18-13 >>] and the like. A common monomer used for surface-hydrophilization of polymer materials by graft polymerization is vinyl monomer (eg acrylic acid, 2-
Hydroxyethyl acrylate, acrylamide, N,
N-dimethylacrylamide, etc.). For example, Lawler et al. [Radiation Physics and Chemistry (Radiat.Phys.Chem.), 15
Vol., P. 595 (1980)] describes graft polymerization of acrylic acid onto polyethylene film for the purpose of obtaining a diaphragm material for batteries, and Rai et al. [Physicochemical Aspects of
Polymer Surfaces (Physicochemical Aspects of P
olymer Surfaces), Volume 2 (KLMittal Ed., Plenum, New
(York) (1983) pp. 923-941] shows that when acrylamide is graft-polymerized on a high-density polyethylene film and a low-density polyethylene film, the contact angle of ungrafted polyethylene with water is almost 90 degrees. It was shown that the contact angle decreased with an increase in the amount of polyacrylamide, and the amount of polyacrylamide on the film surface increased. Also, Jansen et al. [J. Biomed. Mater.
Res., 18: 655 (1984)] describes polyurethanes with acrylamide, 2-hydroxyethyl methacrylate,
2,3-epoxypropyl methacrylate (GMA), 2,
After impregnating with 3-hydroxypropyl methacrylate (GOMA), γ-rays from cobalt 60 are irradiated for graft polymerization, and the degree of water swelling increases with an increase in the grafting ratio, especially that polyacrylamide contains a large amount of water. showed that. However, a material obtained by graft-polymerizing acrylic acid exhibits a hydrophilic property as well as an adsorptive property through a water film, resulting in a surface having large slip resistance. Further, the hydrophilicity of the grafted material with a hydrophilic monomer having an ion dissociative group such as acrylic acid shows a tendency such as dissociation in salt solution, aggregation due to salt formation, gelation, etc. It is considered to be affected by the valence of the ions.
On the other hand, when a nonionic amide-type hydrophilic monomer (eg, acrylamide, N, N-dimethylacrylamide) is used, its characteristics are considered to remain unchanged even in a salt solution, but the acrylamide monomer is not toxic as described above. It has a strong drawback, and when N, N-dimethylacrylamide is used as a monomer, it seems that a good hydrophilic surface can be obtained. However, it is limited in application since functional groups available for reaction are scarce.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to improve the appearance, feel, transparency and the like of the original polymer material in a dry state with little or no change in comparison with these known techniques. Another object of the present invention is to provide a novel polymer substance which has extremely strong hydrophilicity when wet with water or body fluids and which has a low friction surface which is not adsorptive. In addition to the physical properties of its surface, such a polymer substance can be further chemically modified on its surface and is suitable for various application developments.

[0009]

[Means for Solving the Problems] The inventors of the present invention have shown that by a surface modification method by graft polymerization, a polymer material has a good hydrophilic surface, that is, "excellent low friction in a wet state with water, In addition, various studies were repeated on a method of providing a surface having a low adsorptivity "(null-null). As a result, when the polymer material and the sugar residue-containing polymerizable monomer are graft-polymerized,
We obtained the knowledge that (1) excellent hydrophilicity (2) low friction without adsorbability can be imparted to polymer materials, and based on this finding, various studies were conducted and the present invention was completed. That is, the present invention is a graft polymer of a polymeric material and a sugar residue-containing polymerizable monomer.

The polymer material that can be used in the present invention is not particularly limited, and any polymer material can be used according to the purpose and application. For example, polyolefins (such as high density polyethylene and low density polyethylene) can be used. , Polypropylene, etc.), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polymethylmethacrylate, styrene-butadiene block copolymer, acrylonitrile-butadiene- Styrene block copolymer, polybutadiene,
Polyisoprene, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyether-ester block copolymers, polycarbonates, polyurethanes (eg polyurethane, polyether urethane, polyurethane urea, etc.), polyamides (eg nylon 6, nylon) 6
6) and polysulfones (for example, polysulfone, polyethersulfone, etc.), silicone, cellulose, cellulose acetate and the like. However, when a graft polymerization method including ozone treatment of a polymer material is adopted, polyurethane (eg, polyurethane, polyether urethane, polyurethane urea, etc.), polyamides (eg, nylon 6, nylon 66, etc.) are used as the polymer material of the base material. ) And polysulfones (eg, polysulfone, polyethersulfone, etc.) and the like are preferable. The form of the substrate to be used may be any form such as non-porous, porous, non-woven fabric, woven fabric, knitted fabric, etc., and the shape may be tubular, cylindrical, sheet-like, plate-like. Any shape such as a block shape, a bead shape, and a fiber shape can be used.

The sugar residue-containing polymerizable monomer used in the present invention is a vinyl monomer having a sugar residue,
That is, the sugar residue vinyl, acryloyl or methacryloyl derivative and the like can be mentioned, but acryloyl or methacryloyl derivative is preferable. Examples of sugar residues include groups derived from monosaccharides, disaccharides and trisaccharides. Examples of the monosaccharide include D-
Glucose, L-glucose, D-galactose, D-mannose, D-fructose, L-fucose, D-glucosamine, N-acetyl-D-glucosamine, N-acetyl-D-galactosamine and the like can be mentioned. Is most preferred. Examples of the disaccharide include lactose, cellobiose, sucrose, maltose and the like, and examples of the trisaccharide include maltotriose and the like. The vinyl, acryloyl or methacryloyl group may be directly bonded to a sugar residue, for example, through a glycosyl bond, or a hydroxyl group or an amino group in the sugar residue, or may be bonded to a suitable spacer group (for example, ethylenediene). Oxy group, oxyethylene amino group, oxyethylene thio group, etc.).
Further, a lactone derivative derived from the above monosaccharide or disaccharide, uronic acid and a ring-opened derivative thereof bound to a vinyl, acryloyl or methacryloyl group (directly or via a spacer group) are also polymerizable monomers of the present invention. Used as. The sugar residue-containing polymerizable monomer used in the present invention is a monomer in which a sugar residue is bonded to the alkyl (eg, ethyl) portion of an alkyl acrylate (eg, ethyl acrylate) or methacrylic acid alkyl ester (eg, ethyl methacrylate). Are particularly preferable, and specific examples of such a polymerizable monomer include 2-glycosylethyl acrylate, 2-glycosylethyl methacrylate (GEMA), 2-galactosylethyl acrylate, 2-galactosylethyl methacrylate, and 2-mannosylethyl acrylate. 2-mannosylethyl methacrylate, 2-xylosylethyl acrylate, 2
-Xylosylethyl methacrylate, N- (4- (α-D-
Glucosyl) phenyl) methacrylamide and the like are mentioned, and GEMA is most preferable. As an example of the polymer using GEMA, Okumura et al. [The 59th Annual Meeting of the Chemical Society of Japan (1
990) Proceedings of the Lecture, p. 1054], reported that a copolymer with acrylamide, acrylonitrile, methyl methacrylate and styrene was prepared, and that a polymer having strong hydrophilicity was obtained as the GEMA content increased. In addition, Ishihara et al. [The 39th Japan Society for Polymer Science (1990) Proceedings, p. 614] synthesized a terpolymer of methacryloyloxyethylphosphorylcholine, butyl methacrylate and GEMA. Although it is acknowledged that there is no case where GEMA was graft-polymerized.

In the present invention, before graft polymerizing the sugar residue-containing polymerizable monomer onto the polymer material, the surface of the polymer material is subjected to a method known per se, for example, the above-mentioned --2.
A polymerization initiation point is introduced by the method of. In particular, it is preferable that the polymer material to be treated is previously exposed to ozone-containing air and a functional group (for example, a hydroperoxy group, a peroxy group, etc.) serving as a starting point of radical polymerization is introduced into the material. Ozone exposure can be conveniently carried out in a suitable container (for example, a glass container such as a desiccator). The concentration of ozone used is not particularly limited, and a gas containing ozone of about 100 to 100,000 ppm that can be prepared by using a commercially available ozone generator is used. In generating ozone, air may be used as the oxygen-containing gas, or pure oxygen may be used to obtain a higher concentration of the ozone-containing gas. The temperature of the ozone treatment may be room temperature or lower, or may be higher than room temperature, but near room temperature
0-30 degreeC) is preferable. The time for ozone treatment of the polymer material is 1 minute to 4 hours, preferably 5 minutes to 2 hours, more preferably 10 to 30 minutes, depending on conditions such as ozone concentration and treatment temperature. Then, the treated material is put into a reaction liquid containing a sugar residue-containing polymerizable monomer,
Deaeration is performed to remove dissolved oxygen, and graft polymerization is caused under deaeration and reduced pressure. As the solvent, water, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, nitriles such as acetonitrile, and mixed solutions thereof are used. When the polymerization reaction is started by heating, the reaction solution is kept at room temperature (about 20 ° C).
The above is heated to a temperature of up to 80 ° C. It is more preferable to heat to 50 to 60 ° C. Further, the graft polymerization may be carried out in the presence of a so-called redox reducing agent. As the redox reducing agent, any agent can be used as long as it can reduce a peroxide group to generate a radical, and examples thereof include ferrous chloride, ferrous sulfate and ferrous sulfate.
Divalent iron salts such as iron ammonium (Mor salt), acidic sodium sulfite, Rongalit, ascorbic acid (salt),
Examples thereof include tartaric acid, and among them, Mohr's salt is preferable.
The amount of the redox reducing agent used varies depending on the compound used, but it is preferable to use an amount that provides a concentration in the range of 10 ⁻⁵ to 10 mol / l, and more preferably 10 ⁻⁴ to 10 ^−2.
It is preferable to use it at a concentration of about mol / l. When a redox reducing agent is used, it is possible to cause the polymerization reaction from a lower temperature than in the case of a thermal reaction, and the usable reaction temperature is from ice cooling (0 ° C.) to 80 ° C., more preferably 5 to It is preferable to select from the range of 60 ° C. The reaction time depends on the reaction temperature, but is 10 minutes to 24 hours, preferably 30 minutes.
Minutes to 2 hours. The optimum range of the graft amount of the sugar residue-containing polymerizable monomer to the polymer material in the graft polymer of the present invention is 5 to 1000 μg / cm ² , more preferably 80 to 1000 μg / cm ² , and most preferably 1
It is from 00 to 900 μg / cm ² .

Graft polymerization may also be carried out under the condition that oxygen is thoroughly removed from the reaction solution, reaction vessel, reaction material, etc. by passing an inert gas (for example, nitrogen, argon etc.) instead of the degassing operation. Good. In that case, the reaction solution and reaction material that have been degassed in advance may be used, and only the inside of the reaction vessel may be replaced with an inert gas to carry out graft polymerization, but it is also possible to bubble the inert gas through the reaction solution. Alternatively, the reaction material may be reacted in a state of being covered with bubbles. In this case, an aqueous solution containing a monomer is preferable as the solvent, and polyvinyl alcohol in an amount of about 0.1% by weight may be added to the reaction solution in order to improve foaming.

After the polymerization reaction for a predetermined time, the polymer material is taken out of the reaction solution and washed with water to remove the by-produced homopolymer to obtain a target surface-modified polymer material.

[0015]

The polymeric material thus obtained is
(1) Excellent hydrophilicity (2) Because it has low friction without adsorbability, it is particularly useful for medical devices / equipment such as container materials (eg blood bags, vacuum pack bags), sheath materials (eg Sheath tubes for mirrors, catheters, etc., tubes for transporting aqueous solutions (eg, tubes for extracorporeal circulation), medical tubes (eg, blood tubes, catheters, etc.), culture media for bacteria and cells, or culture instrument materials (eg, petri dishes). , Vials, etc.), immobilization materials for diagnostic agents and physiologically active substances, etc., as well as clothing materials (eg, watering materials), scale preventive materials (eg, reaction vessel parts, ipsilateral tube tubes, etc.) , Anti-fog materials (eg plastic (underwater) glasses, same side etc.), anti-static materials, anti-fouling materials, toys (eg eel toys,
Widely applicable as a material such as fishing line).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the content of the present invention is not limited to the scope of Examples.

[0017]

【Example】

Example 1 Polyether polyurethane film (Takeda Pharmaceutical Co., Ltd.)
(T-880, 200 micron thick) manufactured by Ozone Generator (O-3-2, manufactured by Nippon Ozone Co., Ltd.) in a desiccator 1
It was exposed to an air atmosphere containing 2800 ppm of ozone for 20 minutes. This film was immersed in a 10% aqueous solution of 2-glycosylethyl methacrylate (GEMA, manufactured by Nippon Seika Co., Ltd.), degassed under reduced pressure, and then heated at 60 ° C. for 1 hour. Then, the film was taken out, washed with water and dried to obtain a polyether polyurethane film grafted with poly-GEMA. In the attenuated total reflection IR spectrum of this film,
3500-3200 cm ^-1 derived from GEMA (hydrogen-bonding O-
A strong absorption band of (H stretching vibration) and an absorption band of C = O stretching vibration of an ester bond were found at 1711 cm ^-1 .

Although the obtained film was indistinguishable from the untreated film when dried, it was well wetted with water when it was put in water, and showed a significantly low friction property in the wet state, and this low friction property was Durability was observed well even after repeated dry-wet.

Example 2 The same polyether polyurethane film as used in Example 1 was treated with ozone in the same manner as in Example 1, and the obtained film was immersed in a 10% aqueous solution of GEMA, and the reaction solution was subjected to Mohr's salt. (Ferrous ammonium sulfate) was added at a concentration of 10 ^-3 molar, degassed under reduced pressure, and then at 60 ° C for 1 hour.
Warmed to. The film was taken out, washed with water and dried to obtain a poly-GEMA-grafted polyether polyurethane film. The obtained film was well wetted with water and showed a significantly low friction property in a wet state.

Example 3 For a tube having an outer diameter of 6 mm and an inner diameter of 4 mm made of polyethylene and nylon, and a tube having an outer diameter of 7 mm and an inner diameter of 4 mm made of polyurethane,
GEMA was graft-polymerized in the same manner as in Example 1 to obtain corresponding poly-GEMA-grafted polyethylene, nylon and polyurethane tubes. It was observed that both the inner surface and the outer surface of the tube were uniformly wet with water, the outer surface showed a significantly low friction, and the inner surface also drained better than the untreated tube.

Example 4-8 Mohr's salt was added to a 10% aqueous solution of GEMA so as to have a concentration of 10 ^-3 mol, and nitrogen gas was aerated to keep foaming. The same polyether polyurethane film used in Example 1 was embedded in the foam, and the film was ozone-treated in the same manner as in Example 1, and the mixture was heated to 35 to 60 ° C. for 2 to 18 hours. Take out the film,
It was washed with water and dried to obtain poly-GEMA-grafted polyether urethane. The obtained film was well wetted with water and showed a significantly low friction property in a wet state.

The graft amount of the obtained film was quantified as follows. That is, first, a 3N HCl solution having a poly GEMA concentration of 0 to 751 μg / ml was heated to 80 ° C. for 4 hours. Next, add 100 μl of the reaction solution to 1
Neutralize with 00 μl of 3N NaOH, add 3 ml of coloring solution (manufactured by Wako Pure Chemical Industries, Ltd., glucose CII-Test Wako for glucose measurement), warm to 37 ° C. for 5 minutes, and then add 505.
The absorbance at nm was measured to obtain a calibration curve. Separately, about 7
The cm ² grafted film was placed in 2 ml of 3N HCl and heated to 80 ° C. for 4 hours. The absorbance of this reaction solution was measured in the same manner as above, and the graft amount per area was determined from the above calibration curve to obtain the results in Table 1.

[0023]

[Table 1]

Example 9 Mohr's salt was added to a 10% aqueous solution of GEMA so as to have a concentration of 10 ^-3 mol, 0.1% by weight of polyvinyl alcohol was further added, and nitrogen gas was bubbled to form bubbles. Kept. The same polyether polyurethane film used in Example 1 was embedded in the foam in the same manner as in Example 1, and the ozone-treated film was embedded for 18 hours.
Warmed to 0 ° C. The film was taken out, washed with water and dried to obtain poly-GEMA-grafted polyether urethane. The obtained film was well wetted with water and showed a significantly low friction property in a wet state.

Claims (1)

[Claims] 1. A graft polymer of a polymeric material and a sugar residue-containing polymerizable monomer.