JPH07184990A - High polymer material for medical treatment and medical treating material - Google Patents

Abstract

PURPOSE:To obtain a high polymer material having excellent compatibility with blood for medical treatment by composing this high polymer material for medical treatment of a linear high polymer having specific value of the content of a phosphorylcholine group-contg. monomer unit, the content of an epoxy group-contg. monomer unit and the content of one kind of monomers among a hydroxyl group-contg. monomer, etc. CONSTITUTION:This high polymer material for medical treatment is composed of the linear high polymer having 5 to 90mol% content of the phosphorylcholine group- contg. monomer unit, 0.01 to 50mol% content of the epoxy group-contg. monomer unit and 0.01 to 50mol% content of at least one kind of the monomer units among the hydroxyl group-contg. monomer, amino group-contg. monomer and carboxyl group- contg. monomer. The surface of a base material is coated with this high polymer material for medical treatment. The high polymer material for medical treatment has excellent compatibility with blood, hardly generates a thrombosis in spite of contact with the blood and hardly generates activation of complement. The medical material coated with this high polymer material for medical treatment is capable of maintaining the compatibility with the blood stably over a long period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical polymer material suitable as a medical material for medical devices, artificial organs, etc., and a medical material excellent in blood compatibility obtained by coating the surface of a substrate with the medical polymer material. Regarding

[0002]

2. Description of the Related Art Recently, medical materials such as artificial organs have been actively developed, but biocompatibility is a problem in this technical field. There is a demand for the development of a medical material having excellent blood compatibility that does not activate blood cells. As a method for obtaining a medical material having excellent blood compatibility, the following three types of methods have been mainly tried. A method of molding using a synthetic polymer having excellent biocompatibility as a raw material, or a method of coating the surface of a medical material with the synthetic polymer. A method of adding an anticoagulant physiologically active substance such as heparin or urokinase to a medical material or binding it to the surface of the medical material. A method using a biomaterial such as collagen or a biovalve as a raw material. In the above methods and, there is a problem that the physiologically active substance or biomaterial used as a raw material is a natural product, which is expensive, and the blood compatibility is lost depending on the manufacturing conditions or storage conditions of the medical material. Therefore, the development of synthetic polymers for medical materials, which can be mass-produced relatively inexpensively and have excellent biocompatibility, is strongly desired and is being actively researched.

Phospholipids are major constituents of biological membranes, are specifically present in the membrane-like structure of cells, and are involved in the function of biological membranes through phospholipids alone or through interaction with membrane proteins. It is known that From this, not only phospholipids but also compounds similar to phospholipids are considered to have excellent biocompatibility and have been actively studied in recent years. For example, in Japanese Patent Laid-Open No. 54-63025,
2-Methacryloyloxyethylphosphorylcholine (hereinafter abbreviated as “MPC”) and a method for producing the same are described, and a polymer of MPC alone and a copolymer of MPC and methyl methacrylate are excellent in biocompatibility. It is shown. Japanese Unexamined Patent Publication (Kokai) No. 3-39309 describes that a copolymer of MPC and methacrylic acid ester is less likely to cause platelet adhesion and aggregation and plasma protein adhesion, and is useful as a medical material.

[0004]

However, the above-mentioned MPC
A single polymer is water-soluble and easily dissolves in contact with body fluids such as blood, so it cannot be used as a medical material. Furthermore, a medical material having a substrate surface coated with a copolymer of MPC and a methacrylic acid ester, which is a hydrophobic monomer, has few problems when used for a short time under conditions where it is in contact with blood, When used for a long time, the copolymer coated on the surface of the base material is gradually eluted into the blood,
There is a drawback that blood compatibility does not last for a long time. Further, since the eluted copolymer may cause an unexpected danger when it enters the body, a safer medical material is required.

A first object of the present invention is to provide a medical polymer material having excellent blood compatibility, which is suitable as a medical material for medical devices, artificial organs and the like. A second object of the present invention is to provide a medical material whose blood compatibility is stably maintained for a long period of time.

[0006]

According to the present invention, the above-mentioned first object is to: (a) contain a phosphorylcholine group-containing monomer unit in an amount of 5 to 90 mol%; The content of the monomer unit is 0.01 to 50 mol%; and (c) the content of at least one kind of monomer unit among a hydroxyl group-containing monomer, an amino group-containing monomer and a carboxyl group-containing monomer It is achieved by providing a medical polymer material comprising a linear polymer in an amount of 0.01 to 50 mol%.

Further, the second object of the present invention is achieved by providing a medical material in which the surface of a substrate is coated with the above-mentioned medical polymeric material.

The medical polymer material of the present invention exhibits blood compatibility by containing a phosphorylcholine group.
The content of the phosphorylcholine group-containing monomer unit is 5 to 90 mol% with respect to the total structural units of the linear polymer.
It is preferably ˜90 mol%. When the content of the phosphorylcholine group-containing monomer unit is less than 5 mol%, blood compatibility is not sufficiently expressed, which is not preferable.

As the phosphorylcholine group-containing monomer,
For example, MPC, 2-methacryloyloxyethoxyethylphosphorylcholine, 6-methacryloyloxyhexylphosphorylcholine, 10-methacryloyloxynonylphosphorylcholine, allylphosphorylcholine, butenylphosphorylcholine, hexenylphosphorylcholine,
Examples thereof include octenylphosphorylcholine and decenylphosphorylcholine. Among them, MPC is preferable because it has excellent polymerizability and is easily available.
These phosphorylcholine group-containing monomers are used alone or in combination of two or more.

The content of the epoxy group-containing monomer unit is 0.01 to 50 mol%, preferably 0.1 to 50 mol% based on the total structural units of the linear polymer. If the structural unit is less than 0.01 mol%, the cross-linking bond between linear polymers and the bond between the linear polymer and the surface of the base material become weak, so the surface was coated with the medical polymer material of the present invention. It is not preferable that the medical material comes into contact with water, blood or the like, because the medical polymer material is easily detached from the surface of the base material. Further, when the structural unit exceeds 50 mol%, the cross-linking bond between the linear polymers becomes very strong and the degree of freedom of the phosphorylcholine group decreases, so that the blood compatibility derived from the phosphorylcholine group is hard to be expressed. It tends to become unfavorable.

As the epoxy group-containing monomer, for example,
Glycidyl acrylate, glycidyl methacrylate,
Allyl glycidyl ether etc. can be mentioned. Of these, glycidyl methacrylate is preferable because it has excellent copolymerizability with MPC and is easily available. These epoxy group-containing monomers are used alone or in combination of two or more.

The content of at least one of the hydroxyl group-containing monomer, amino group-containing monomer and carboxyl group-containing monomer is 0 based on the total structural units of the linear polymer. It is 0.01 to 50 mol%, preferably 0.1 to 50 mol%. 0.01 mol% of the structural unit
In the case of less than, cross-linking between linear polymers, the bond between the linear polymer and the substrate surface is weak, when the medical material whose surface is coated with the medical polymeric material of the present invention comes into contact with water, blood, etc. It is not preferable because the medical polymer material is easily detached from the surface of the substrate. Further, when the structural unit exceeds 50 mol%, the cross-linking bond between the linear polymers becomes very strong and the degree of freedom of the phosphorylcholine group decreases, so that the blood compatibility derived from the phosphorylcholine group is hard to be expressed. It tends to become unfavorable.

As the hydroxyl group-containing monomer, for example, 2-
Examples thereof include hydroxyethyl (meth) acrylate, allyl alcohol, 2-allylphenol, glycerol α-monoallyl ether, ethylene glycol monoallyl ether, N- (hydroxymethyl) acrylamide, and 2-hydroxypropyl (meth) acrylate. . Among them, 2-hydroxyethyl methacrylate is preferable because it has excellent bonding properties with epoxy groups and is easily available. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the amino group-containing monomer include allylamine, allylurea, 1-allyl-2-thiourea, 2-methylallylamine and the like.
Of these, allylamine is preferable because it is excellent in the bondability with the epoxy group and is easily available. These amino group-containing monomers are used alone or in combination of two or more.

As the carboxyl group-containing monomer, for example, acrylic acid, methacrylic acid, 3-pentenoic acid, 4-
Pentenoic acid, 3-allyloxypropionic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid and the like can be mentioned. Among them, acrylic acid is preferable because of its excellent bondability with an epoxy group and its easy availability. These carboxyl group-containing monomers are used alone or in combination of two or more.

The medical polymer material of the present invention includes other than the above-mentioned phosphorylcholine group-containing monomer, epoxy group-containing monomer, hydroxyl group-containing monomer, amino group-containing monomer and carboxyl group-containing monomer. In addition, it can be produced by using other copolymerizable monomer. The copolymerizable monomer unit is preferably contained in an amount of 0 to 90 mol%, more preferably 10 to 75 mol%, based on the total structural units of the linear polymer. Other copolymerizable monomers that can be used in the present invention include, for example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and hexyl methacrylate; vinyl chloride, acrylonitrile, vinylpyrrolidone. And copolymerizable monomers such as styrene. Among them, when a proper amount of hydrophobic monomers such as methyl methacrylate and n-butyl methacrylate is contained, the resulting medical polymer material and unpolymerized monomer are produced during the production of the medical polymer material. It is preferable in that the separation and purification step of (3) becomes easy. These copolymerizable monomers are used alone or in combination of two or more.

The medical polymer material of the present invention is, for example, a phosphorylcholine group-containing monomer; an epoxy group-containing monomer;
And polymerizing a monomer mixture containing at least one kind of monomer containing a hydroxyl group, an amino group and a carboxyl group in a solvent in the presence of a polymerization initiator. Is obtained by

The solvent may be any solvent in which the monomer can be dissolved, and examples thereof include methanol, ethanol, t-butyl alcohol, benzene, toluene, tetrahydrofuran, dioxane, dichloromethane and chloroform. These solvents are used alone or in combination of two or more.

The polymerization initiator may be any ordinary radical initiator, for example, 2,2'-azobisisobutylnitrile (hereinafter abbreviated as "AIBN"),
Examples thereof include azo compounds such as 1,1′-azobis (cyclohexane-1-carbonitrile) and organic peroxides such as benzoyl peroxide and lauryl peroxide.

The medical polymer material of the present invention can be obtained in various molecular weights depending on the purpose of use. In the production of the medical polymer material, the obtained medical polymer material and an unpolymerized monomer are used. From the viewpoint of facilitating the step of separation and purification from the body, the number average molecular weight is preferably 5,000 or more, more preferably 10,000 or more.

Although the medical polymer material of the present invention can be molded to obtain a medical material, it can be easily converted into a medical material by coating the surface of a base material of a commercially available medical material with the medical polymer material. It is possible to impart blood compatibility.

The coating of the medical polymer material on the surface of the substrate is
For example, a solution is prepared by dissolving the medical polymer material in an organic solvent to have a concentration of 1 to 10% by weight, and the solution is applied to the substrate surface by a known method such as dipping or spraying,
It is carried out by drying at room temperature or under heating.

As the organic solvent, one that does not modify the surface of the base material of the medical material is used. For example, methanol,
A single solvent such as ethanol, dioxane, or acetone or a mixed solvent thereof is used. Of these, methanol and ethanol are preferable because they do not denature the surface of the base material of ordinary medical materials and have a low boiling point, which facilitates drying.

The coating amount of the medical polymer material on the surface of the substrate is preferably 10 ^-10 to 10 ^-5 mol of phosphorylcholine group per 1 cm ^{2 of the} surface of the substrate, and 10 ^-9 to 1
It is more preferably 0 ^-5 mol. When the phosphorylcholine group is less than 10 ^-10 mol per 1 cm ^{2 of the} surface of the substrate, blood compatibility is not sufficiently exhibited, which is not preferable.

As the above-mentioned base material, any known medical material can be used without any problem, and in particular, a base material having a hydroxyl group, an amino group, a carboxyl group or the like capable of covalently bonding with an epoxy group. Is preferred. Moreover, when using what does not have the group which can couple | bond with an epoxy group on the surface of a base material, it is preferable to use after introduce | transducing a hydroxyl group etc. to the surface of a base material by an oxidation process etc. Examples of such a base material include polyurethanes and polyvinyl chlorides used in blood bags, blood circuits, catheters and the like; polycarbonates used in syringes and containers, acrylics such as methylmethacrylate, and the like. Polyolefins such as polypropylene; polyamides such as nylon used in artificial blood vessels, etc .; polysulfones used in blood treatment membranes such as artificial kidneys, celluloses such as cellulose and cellulose acetate, ethylene-vinyl alcohol, etc. The polyvinyl alcohols can be mentioned.

The oxidation treatment of the surface of the base material can be carried out by a known method. For example, a method of performing plasma treatment in a gas containing oxygen gas or a method of chemically treating with a sulfuric acid solution containing permanganate or the like can be mentioned. The method of plasma treatment is preferable because a large amount of medical material can be treated in a short time and the medical material can be kept clean because it is treated in a gas. The method of chemical treatment is
It has a wide range of applications because it can process even those with complicated shapes and those that cannot be plasma-processed such as the inner surface of the container. In general, medical materials that come into contact with blood often have complicated shapes such as tubes, hollow fibers and bottles.
The method of chemical treatment is advantageous.

The epoxy group in the medical polymer material is removed by applying a solution in which the medical polymer material of the present invention is dissolved onto the surface of the substrate, followed by drying and heat treatment. Crosslinks with hydroxyl, amino or carboxyl groups in molecular materials. Furthermore, if hydroxyl groups, amino groups, carboxyl groups, etc. are present on the surface of the base material, the epoxy groups in the medical polymer material should crosslink with these groups on the surface of the base material and bond to the surface of the base material by covalent bonding. You can Since the covalent bond formed by thermal crosslinking has a property of being hardly hydrolyzed, the medical polymer material coated on the surface of the base material is not easily detached. The heat treatment temperature varies depending on the material of the medical material used, but is generally within a temperature range where the medical material is not denatured by heat, 60 to 160 ° C.
Are preferable, and 70-140 degreeC is more preferable. The heat treatment time is preferably 30 minutes to 24 hours.

The medical polymer material of the present invention is excellent in blood compatibility, and even when it is brought into contact with blood, thrombus is unlikely to occur and complement activation is unlikely to occur. In addition, a medical material whose surface is coated with the medical polymer material is a blood-compatible material because the medical polymer material with excellent blood compatibility coated on the surface of the substrate does not easily detach. The sex is retained for a long time. Therefore, the medical material of the present invention comprises a catheter,
It is suitable as a material for all medical devices such as blood circuits, blood bags, hemodialysis membranes, artificial blood vessels, etc., which are used in contact with blood for a long time.

[0029]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto. In the following examples, the number average molecular weight of the obtained medical polymer material is GP.
It was determined from the standard polystyrene calibration curve by method C. The content ratio of each structural unit in the medical polymer material is ¹ H-NM
It was determined by the R method.

Example 1 MPC [manufactured by NOF CORPORATION] 2.0 g (35 mol%),
Glycidyl methacrylate 0.03 g (1 mol%), n-butyl methacrylate 1.52 g (55 mol%), 2-hydroxyethyl methacrylate 0.22 g (9 mol%)
And AIBN (0.04 g) were dissolved in 28 ml of ethanol, and the inside of the reaction vessel was sufficiently replaced with argon gas.
The polymerization reaction was carried out by immersing the reaction container in a warm bath at 60 ° C. for 24 hours. After cooling, the polymerization solution was poured into chloroform to precipitate the polymer. The precipitate separated by filtration was dissolved in methanol and then poured into chloroform again to precipitate the polymer, which was repeated twice. Finally, the precipitate was replaced with chloroform and precipitated with ethyl ether. Dried. The yield was 95%. The content of the phosphorylcholine group-containing monomer unit, the epoxy group-containing monomer unit, the hydroxyl group-containing monomer unit in the obtained medical polymer material, and the number average molecular weight of the medical polymer material are shown in Table 1 below. Shown in.

Example 2 MPC 4.0 g (65 mol%), glycidyl methacrylate 0.60 g (0.2 mol%), n-butyl methacrylate 0.58 g (19.8 mol%) , 2-hydroxyethyl methacrylate 0.40
g (15 mol%), a medical polymer material was obtained in the same manner as in Example 1 except that AIBN was changed to 0.08 g. The yield was 90%. The content of the phosphorylcholine group-containing monomer unit, the epoxy group-containing monomer unit, the hydroxyl group-containing monomer unit in the obtained medical polymer material, and the number average molecular weight of the medical polymer material are shown in Table 1 below. Shown in.

Example 3 MPC 2.0 g (35 mol%), glycidyl methacrylate 0.03 g (1 mol%), n-butyl methacrylate 1.52 g (55 mol%), acrylamide 0. A medical polymer material was obtained in the same manner as in Example 1 except that 125 g (9 mol%) was used. The yield was 60%. Phosphorylcholine group-containing monomer unit in the obtained medical polymer material, epoxy group-containing monomer unit, content of amino group-containing monomer unit,
The number average molecular weights of the medical polymer materials are shown in Table 1 below.

Example 4 MPC 4.0 g (60 mol%), glycidyl methacrylate 0.14 g (0.5 mol%), n-butyl methacrylate 0.88 g (27.5 mol%) , Acrylamide 0.19 g (12 mol%), A
A medical polymer material was obtained in the same manner as in Example 1 except that IBN was replaced with 0.08 g. The yield was 65%. The following table shows the content of the phosphorylcholine group-containing monomer unit, the epoxy group-containing monomer unit, the amino group-containing monomer unit, and the number average molecular weight of the medical polymer material in the obtained medical polymer material. Shown in 1.

Example 5 MPC 2.0 g (35 mol%), glycidyl methacrylate 0.03 g (1 mol%), n-butyl methacrylate 1.52 g (55 mol%), acrylic acid 0 A medical polymer material was obtained in the same manner as in Example 1 except that the amount was changed to 127 g (9 mol%).
The yield was 70%. The following table shows the content of the phosphorylcholine group-containing monomer unit, the epoxy group-containing monomer unit, the carboxyl group-containing monomer unit in the obtained medical polymer material, and the number average molecular weight of the medical polymer material. Shown in 1.

Example 6 MPC 4.0 g (50 mol%), glycidyl methacrylate 0.08 g (2 mol%), n-butyl methacrylate 1.46 g (38 mol%), acrylic acid 0 .19 g (10 mol%), AIBN
A medical polymer material was obtained in the same manner as in Example 1 except that 0.08 g was used instead. The yield was 67%. The following table shows the content of the phosphorylcholine group-containing monomer unit, the epoxy group-containing monomer unit, the carboxyl group-containing monomer unit in the obtained medical polymer material, and the number average molecular weight of the medical polymer material. Shown in 1.

Comparative Example 1 MPC 5.0 g (35 mol%) and n-butyl methacrylate 5.2 g (65 mol%) were used instead of the respective monomers, and the polymerization solvent was 21.0 ml of methanol and THF 2.
A medical polymer material containing no epoxy group was obtained in the same manner as in Example 1 except that the mixed solvent was changed to 9.0 ml. The yield was 83%. Content of the phosphorylcholine group-containing monomer unit in the obtained medical polymer material,
The number average molecular weights of the medical polymer materials are shown in Table 1 below.

Comparative Example 2 Example 1 except that the proportions of the respective monomers used were changed to 3.0 g (99 mol%) of 2-hydroxyethyl methacrylate and 0.03 g (1 mol%) of glycidyl methacrylate.
In the same manner as above, a medical polymer material containing no phosphorylcholine group was obtained. The yield was 78%. The content of the hydroxyl group-containing monomer unit and the epoxy group-containing monomer unit in the obtained medical polymer material and the number average molecular weight of the medical polymer material are shown in Table 1 below.

[0038]

[Table 1]

Example 7 Using a polypropylene test tube having a capacity of 15 ml, the inner surface of the test tube was coated with the medical polymer material obtained in Example 1 according to the following method. The test tube was immersed in a solution prepared by dissolving the medical polymer material obtained in Example 1 in an ethanol solution to a concentration of 5% for about 1 minute, and dried with a ventilation dryer at 30 ° C. After repeating this operation 3 times, it was heat-treated at 140 ° C. for 2 hours to obtain a test tube coated with the medical polymer material. The amount of phosphorylcholine groups on the surface of the substrate was measured by X-ray elemental analysis, and was 4 × 10 ⁻⁶ mol / cm ² . 2 ml of fresh blood from a healthy person was poured into this test tube, the state of blood was observed every 30 seconds, and the time at which the fluidity of blood was lost (coagulation time) was measured, and it was about 24 minutes.

Example 8 A test tube was coated with the medical polymer material obtained in Example 2 in the same manner as in Example 7, and the blood coagulation time was measured to be about 22 minutes.

Example 9 A test tube was coated with the medical polymer material obtained in Example 3 in the same manner as in Example 7, and the blood coagulation time was measured to be about 23 minutes.

Example 10 A test tube was coated with the medical polymer material obtained in Example 4 in the same manner as in Example 7, and the blood coagulation time was measured to be about 22 minutes.

Example 11 A test tube was coated with the medical polymer material obtained in Example 5 in the same manner as in Example 7, and the blood coagulation time was measured to be about 20 minutes.

Example 12 A test tube was coated with the medical polymer material obtained in Example 6 in the same manner as in Example 7, and the blood coagulation time was measured to be about 21 minutes.

Comparative Example 3 Using a test tube not coated with a medical polymer material,
When the blood coagulation time was measured by the same method as in Example 7, it was about 14 minutes.

Example 13 The medical polymer material obtained in Example 1 was coated with acrylic beads in the same manner as in the coating method for a test tube in Example 7 to heat-treat at 140 ° C. for 2 hours. ,
Acrylic beads coated with a medical polymer material were obtained.
When the amount of phosphorylcholine groups on the surface of the substrate was measured by X-ray elemental analysis, it was 3.5 × 10 ⁻⁶ mol / cm ² . A column with an inner diameter of 4 mm and a length of 65 mm was filled with acrylic beads coated with a medical polymer material, and then healthy human whole blood containing sodium citrate as an anticoagulant was applied to the column at a flow rate of about 0.25 ml / min. Poured. After 30 minutes from the start of blood flow, about 0.3 ml of whole blood at the inlet and outlet of the column was collected and fixed with glutaraldehyde, and then the number of platelets was measured with a Coulter counter, and the platelet passage rate was calculated by the following formula 1. The platelet passage rate is shown in Table 2 below.

[0047]

[Equation 1]

Example 14 The medical polymer material obtained in Example 2 was coated on acrylic beads in the same manner as in Example 13, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Example 15 The acrylic polymer beads coated with the medical polymer material obtained in Example 3 by the same operation as the coating method for a test tube performed in Example 7 were heat treated at 80 ° C. The passage rate of platelets was measured in the same manner as in 13. The platelet passage rate is shown in Table 2 below.

Example 16 The medical polymer material obtained in Example 4 was coated on acrylic beads in the same manner as in Example 15, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Example 17 The medical polymeric material obtained in Example 5 was coated on acrylic beads in the same manner as in Example 15, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Example 18 The medical polymer material obtained in Example 6 was coated on acrylic beads in the same manner as in Example 15, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Comparative Example 4 The medical polymer material obtained in Comparative Example 1 was coated on acrylic beads in the same manner as in Example 13, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Comparative Example 5 The medical polymer material obtained in Comparative Example 2 was coated on acrylic beads in the same manner as in Example 13, and then the platelet passage rate was measured. The platelet passage rate is shown in Table 2 below.

Comparative Example 6 Acrylic beads not coated with a medical polymer material
After heat treatment at 40 ° C., the platelet passage rate was measured by the same method as in Example 13. The platelet passage rate is shown in Table 2 below.

[0056]

[Table 2]

Example 19 A polyvinyl chloride tube (inner diameter: 3 mm) widely used as a blood circuit was used, and the inner surface of the tube was coated with the medical polymer material obtained in Example 1 according to the following method.
50% sulfuric acid aqueous solution containing 1% potassium permanganate,
After circulating in a polyvinyl chloride tube for 5 minutes, distilled water was caused to flow for 10 minutes for washing and drying to obtain a polyvinyl chloride tube having hydroxyl groups introduced on the inner surface. A solution obtained by dissolving the medical polymer material obtained in Example 1 so as to have a concentration of 5% in a 95% ethanol solution was circulated for 5 minutes in a polyvinyl chloride tube having hydroxyl groups introduced on the inner surface. 80 ℃ after drying at room temperature
A polyvinyl chloride tube coated with a medical polymer material was obtained by heating for 2 hours. When the amount of phosphorylcholine groups on the surface of the substrate was measured by X-ray elemental analysis, it was 3 × 10 ⁻⁶ mol / cm ² . This vinyl chloride tube was cut into a piece having a length of 5 cm, and the tube was embedded so as to replace a part of the abdominal aorta of the rabbit. Two days later, the polyvinyl chloride tube embedded in the rabbit was taken out and fixed with glutaraldehyde, and then the tube inner surface was observed with an electron microscope. As a result, only a slight amount of protein was attached.

Comparative Example 7 A vinyl chloride tube in which the inner surface of the tube was just washed with an ethanol solution was embedded in a rabbit in the same manner as in Example 19, and then the inner surface of the tube was observed with an electron microscope. Was adhered in a large amount, and the formation of white thrombus was considerably advanced.

[0059]

Industrial Applicability The polymer material for medical use of the present invention is excellent in blood compatibility, and even when it is brought into contact with blood, thrombus hardly occurs and complement activation hardly occurs. In addition, the medical material whose surface is coated with the medical polymer material does not easily come off because the medical polymer material with excellent blood compatibility coated on the surface of the base material is not easily detached. Is stably maintained for a long period of time.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tatsuhiko Higaki 1-1239 Umeda, Kita-ku, Osaka Kuraray Co., Ltd. (72) Toru Wada 1-1239 Umeda, Kita-ku, Osaka Kuraray Co., Ltd. Within

Claims (2)

[Claims] 1. A content of (a) a phosphorylcholine group-containing monomer unit is 5 to 90 mol%; (b) a content of an epoxy group-containing monomer unit is 0.01 to 50 mol%; ) A medical treatment comprising a linear polymer in which the content of at least one kind of monomer unit among a hydroxyl group-containing monomer, an amino group-containing monomer and a carboxyl group-containing monomer is 0.01 to 50 mol%. Polymer materials for. 2. A medical material in which the surface of a base material is coated with the medical polymer material according to claim 1.