JPH0751355A - Medical synthetic high polymer and medical material - Google Patents

Abstract

PURPOSE:To obtain a medical synthetic high polymer having excellent blood compatibility by processing a medical synthetic high polymer having a specific phosphoryl choline group content, and a specific content of a silane-containing monomer unit which produces silanol groups when subjected to hydrolysis. CONSTITUTION:A synthetic high polymer having a phosphoryl choline group content in the range of 5 to 90 mol.% and a content of a silane-containing monomeric unit which produces silanol groups when subjected to hydrolysis in the range of 0.01 to 10 mol.% is used as a medical material or is used for coating the surface of a foundation to produce a medical material. The medical synthetic high polymer has excellent blood compatibility and scarcely form thrombi when blood is brought into contact therewith. A medical coated with the medical synthetic high polymer film maintains blood compatibility stably for a long period of use because the medical synthetic high polymer film will not easily come off.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic polymer suitable for medical materials such as medical devices and artificial organs, and a medical material having a substrate surface coated with the synthetic polymer and having excellent blood compatibility. .

[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. The above methods and methods have problems that the physiologically active substances and biomaterials used as raw materials are natural products and are expensive, and that blood compatibility is lost depending on the manufacturing conditions or storage conditions of the medical materials. 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 Patent Application Laid-Open No. 3-39309 discloses that
The copolymer of MPC and methacrylic acid ester is less likely to cause platelet adhesion and aggregation and plasma protein adhesion,
It is described as being 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 synthetic polymer for medical materials, which is suitable for medical materials such as medical devices and artificial organs and has excellent blood compatibility. 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]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a monomer consisting of a phosphorylcholine group-containing monomer and a silane-containing monomer that produces a silanol group by hydrolysis. The present invention has been found out that a medical material having a substrate surface coated with a copolymer of a body mixture retains blood compatibility for a long period of time.

According to the present invention, the above first object is that the content of the phosphorylcholine group is 5 to 90 mol% and the content of the silane-containing monomer unit that produces a silanol group by hydrolysis is 0.01 to. This is achieved by providing a synthetic polymer for medical materials that is 10 mol%.

The second object of the present invention is achieved by providing a medical material in which the surface of a base material is coated with the above-mentioned synthetic polymer for medical material.

The synthetic polymer for medical materials of the present invention exhibits blood compatibility by containing a phosphorylcholine group. The content of the phosphorylcholine group is 5 to 90 mol%, preferably 25 to 90 mol%. When the content of the phosphorylcholine group 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 silane-containing monomer unit which produces a silanol group by hydrolysis is obtained by polymerizing a compound having both a polymerizable double bond-containing group and a silane group which produces a silanol group by hydrolysis. Examples of the polymerizable double bond-containing group include a vinyl group, a (meth) acryloxy group, a (meth) acrylamide group and the like. Of these, a (meth) acryloxy group is preferable because of its excellent copolymerizability with MPC. A silane group that produces a silanol group by hydrolysis is a group that is easily hydrolyzed when it comes into contact with water to produce a silanol group, such as a halogenated silane group, an alkoxysilane group, a phenoxysilane group, and an acetoxysilane. A group etc. can be mentioned. Of these, a halogenated silane group and an alkoxysilane group are preferable because they easily generate a silanol group.

Examples of the above-mentioned silane-containing monomer include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyltriacetoxysilane and vinyl. Triphenoxysilane, vinyltriisopropoxysilane, vinyltris (β-methoxyethoxy) silane,
Vinylisobutyldimethoxysilane, vinylmethoxydibutoxysilane, vinyltrihexyloxysilane, vinyltrioctyloxysilane, vinylmethyldilauryloxysilane, allyltrichlorosilane, phenylallyldichlorosilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyl Vinylsilane compounds such as triethoxysilane, allyldimethylethoxysilane, 3-butenyltrimethoxysilane, 5-hexenyldimethylchlorosilane, 7-octenyltrichlorosilane, 19-dodecanyltrimethoxysilane, and styrylethyltrimethoxysilane; 3- (Meth) acryloxypropenyltrimethoxysilane, 3- (meth) acryloxypropylbis (trimethylsiloxy) methylsilane, 3- (meth) ac Roxypropyldimethylchlorosilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropylmethyldichlorosilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyl Trichlorosilane, 3- (meth) acryloxypropyltribromosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltris (methoxyethoxy) silane, 8- (meth) acryloxyoctani Lutrimethoxysilane, 11
-(Meth) acryloxyundenyltrimethoxysilane and other (meth) acryloxyalkylsilane compounds; 3-
(Meth) acrylamidopropyltrimethoxysilane,
3- (meth) acrylamidopropyltriethoxysilane, 3- (meth) acrylamidetris (β-methoxyethoxy) silane, 2- (meth) acrylamidoethyltrimethoxysilane, 3- (meth) acrylamidopropyltriacetoxysilane, 4- (Meth) acrylamidobutyltriacetoxysilane, 3- (N-methyl-)
(Meth) acrylamidosilane compounds such as (meth) acrylamide) propyltrimethoxysilane, 2- (N-methyl- (meth) acrylamide) ethyltriacetoxysilane, and 2- (meth) acrylamido-2-methylpropylchlorodimethoxysilane. Can be mentioned. Among them, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane are preferable from the viewpoint of excellent copolymerizability with MPC and the ease of availability. . These silane-containing monomers are
Used alone or in combination of two or more.

The synthetic polymer for medical materials according to the present invention contains 0.01 to 10 mol% of silane-containing monomer units which generate silanol groups by hydrolysis, and 0.1 It is preferably contained at 10 to 10 mol%. If the structural unit is less than 0.01 mol%, the silanol groups produced by hydrolysis are small, so that the cross-linking bond between the copolymers and the bond between the synthetic polymer and the substrate surface are weak, and the synthetic polymer is It is not preferable because it comes off easily when it comes into contact with blood or the like. Further, when the structural unit exceeds 10 mol%, the cross-linking bond between the copolymers 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.

The synthetic polymer for medical materials of the present invention can be produced by using other copolymerizable monomers in addition to the phosphorylcholine group-containing monomer and the above silane-containing monomer. The copolymerizable monomer unit is 0 for all structural units.
˜95 mol% is preferred, 10 to 75
It is more preferable that the content is mol%. Other copolymerizable monomers that can be used in the present invention include, for example, methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, hexyl methacrylate, and 2-hydroxyethyl methacrylate. Examples thereof include vinyl chloride, acrylonitrile, vinylpyrrolidone, styrene, vinyl acetate, and other copolymerizable monomers. Above all, when a suitable amount of hydrophobic monomers such as methyl methacrylate and n-butyl methacrylate is contained,
It is preferable because the step of separating and purifying the obtained synthetic polymer and unpolymerized monomer becomes easy. These copolymerizable monomers are used alone or in combination of two or more.

The synthetic polymer for medical materials of the present invention comprises, for example, a monomer mixture containing a phosphorylcholine group-containing monomer and the above silane-containing monomer in the presence of a polymerization initiator.
Obtained by polymerizing in a solvent.

Any solvent can be used as long as it can dissolve the monomer, 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 referred to as "AIBN"), 1,1 '.
Examples thereof include azo compounds such as -azobis (cyclohexane-1-carbonitrile), organic peroxides such as benzoyl peroxide and lauryl peroxide, and the like.

The synthetic polymer for medical materials of the present invention can be obtained in various molecular weights depending on the purpose of use, but it is easy to separate and purify the obtained synthetic polymer and unpolymerized monomer. The number average molecular weight is preferably 5,000 or more, and 1
It is more preferably 0000 or more.

Although the synthetic polymer itself for medical materials 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 synthetic polymer. It is possible to impart blood compatibility.

For coating the surface of the base material with the synthetic polymer for medical materials, for example, a solution is prepared by dissolving the synthetic polymer in an organic solvent containing a small amount of water to a concentration of 1 to 10% by weight. It is carried out by coating on the surface of the substrate by a known method such as dipping, spraying, etc., and then drying at room temperature or under heating. Hydrolysis occurs due to water contained in the organic solvent, and silanol groups are formed in the synthetic polymer. When the water content is low, the silanol groups are not sufficiently formed, and the cross-linking bond or the bond between the synthetic polymer and the base material becomes weak. On the other hand, as the water content increases, it takes longer to dry. Theoretically, it suffices that the water necessary for producing a silanol group by hydrolysis is contained, but considering the ease of preparing the solution, a water content of about 1 to 5% is preferable.

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 synthetic polymer for medical materials on the surface of the base material is preferably 10 ^-10 to 10 ^-5 mol of phosphorylcholine groups per cm ^{2 of the} surface of the base material, preferably 10 ^-9.
More preferably, it is from 10 to ⁵ mol. Base material surface 1 cm
^{When the} phosphorylcholine group per ² is less than 10 ^-10 mol, 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 group such as a hydroxyl group capable of covalently bonding with a silanol group is preferable.
Further, it is also possible to use one having no hydroxyl group-bonding group on the surface thereof and having a hydroxyl group introduced by oxidation treatment. 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, glasses; 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 Examples thereof include polyvinyl alcohols such as alcohol.

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.

In the step of applying the solution in which the synthetic polymer for medical materials of the present invention is dissolved to the surface of the substrate and then drying it, the silanol groups in the synthetic polymer are combined with other silanol groups in the synthetic polymer. Or a hydroxyl group in the synthetic polymer,
It dehydrates and condenses with amino groups to form crosslinks and gel. Furthermore, if hydroxyl groups, carbonyl groups, amino groups, amide groups, etc. are present on the surface of the base material, the silanol groups in the synthetic polymer dehydrate and condense with these groups on the surface of the base material and bond to the surface of the base material by covalent bonding. can do. Since the covalent bond formed by the dehydration condensation of the silanol group has a property of being hardly hydrolyzed, the synthetic polymer coated on the surface of the base material is not easily released. The dehydration condensation of silanol groups is accelerated by heat treatment. It is preferable to perform heat treatment within a temperature range where the medical material is not denatured by heat, for example, at 60 to 120 ° C. for 30 minutes to 24 hours.

The synthetic polymer for medical materials of the present invention is excellent in blood compatibility, and is unlikely to cause thrombus even when contacted with blood.
Complement activation is also unlikely to occur. In addition, the medical material whose surface is coated with the synthetic polymer for medical materials does not easily release the synthetic polymer with excellent blood compatibility coated on the surface of the base material. Is retained for a long time. Therefore, the medical material of the present invention is suitable as a material for all medical devices such as catheters, blood circuits, blood bags, hemodialysis membranes, artificial blood vessels, etc., which are used in contact with blood for a long period of time.

[0027]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto.

Example 1 MPC [manufactured by NOF Corporation] 13.23 g (45 mol%), 3-methacryloxypropyltrimethoxysilane 0.124 g (0.5 mol%), n-butyl methacrylate 6. 32 g (44.5 mol%), 2-hydroxyethyl methacrylate 1.3 g (10 mol%) and AIBN
0.1 g was dissolved in a mixed solution of 40 ml of methanol and 60 ml of tetrahydrofuran, 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. The precipitate of the polymer was separated by filtration and dried under vacuum. And dried. The yield was 50%. The content of the phosphorylcholine group and the silane-containing monomer unit in the obtained synthetic polymer and the number average molecular weight of the synthetic polymer were as shown in Table 1 below. The content of the phosphorylcholine group and the silane-containing monomer unit in the synthetic polymer was determined by proton NMR. Based on the hydrogen (about 1 ppm) of the methyl group of methacrylic acid, the content of the phosphorylcholine group was calculated from the hydrogen (2.95 ppm) of the methyl group and methylene group on the carbon directly bonded to the nitrogen atom. The content of the monomer unit was determined from the hydrogen of the methoxy group of the silyl group (3.1 ppm). The number average molecular weight of the synthetic polymer was determined from the standard polystyrene calibration curve by the GPC method.

Example 2 The proportion of each monomer used was 8.82 g (30 mol%) of MPC, 0.18 g (0.5 mol%) of 11-methacryloxyundenyltrimethoxysilane, and 6.0 g (60%) of methyl methacrylate. Mol%) and 2-hydroxypropyl methacrylate (1.22 g, 9.5 mol%) were used instead, and a synthetic polymer was obtained in the same manner as in Example 1. Yield 6
It was 2%. The content of the phosphorylcholine group and the silane-containing monomer unit in the obtained synthetic polymer and the number average molecular weight of the synthetic polymer were as shown in Table 1 below.

Example 3 The proportions of the respective monomers used were MPC 23.52 g (80 mol%), methacryloxypropyltrichlorosilane 1.
31 g (5 mol%), n-butyl methacrylate 2.13 g
A synthetic polymer was obtained in the same manner as in Example 1 except that (15 mol%) was used. The yield was 35%. The content of the phosphorylcholine group and the silane-containing monomer unit in the obtained synthetic polymer and the number average molecular weight of the synthetic polymer were as shown in Table 1 below.

Comparative Example 1 MPC 8.82 g (30 mol%), methyl methacrylate 6.0 g (60 mol%), 2
-Hydroxypropyl methacrylate 1.22 g (10
Mol%) and no silane-containing monomer was used to obtain a synthetic polymer in the same manner as in Example 1. The yield was 57%. The content of the phosphorylcholine group in the obtained synthetic polymer and the number average molecular weight of the synthetic polymer were as shown in Table 1 below.

Comparative Example 2 Except that the ratio of each monomer used was changed to MPC 23.52 g (84 mol%) and n-butyl methacrylate 2.13 g (16 mol%), and no silane-containing monomer was used. A synthetic polymer was obtained in the same manner as in Example 1. Yield 62
%Met. The content of the phosphorylcholine group in the obtained synthetic polymer and the number average molecular weight of the synthetic polymer were as shown in Table 1 below.

[0033]

[Table 1]

Example 4 A test tube for aggregation (glass tube) having an inner diameter of 10 mm was used, and the inner surface of the test tube for aggregation was coated with the synthetic polymer obtained in Example 1 according to the following method. The aggregating test tube was immersed in a solution of the synthetic polymer obtained in Example 1 in methanol / water / acetic acid (95 / 4.5 / 0.5) at a concentration of 3% for 10 minutes, After drying at room temperature, heat treatment was performed at 80 ° C. for 12 hours to obtain a test tube for aggregation coated with a synthetic polymer. When the amount of phosphorylcholine groups on the surface of the substrate was measured by X-ray elemental analysis, it was 6 × 10 ^-7 mol /
It was cm ² . 1 m of fresh adult blood in this agglutination test tube
When l was poured, the condition of blood was observed every minute, and the time (coagulation time) at which the fluidity of blood was lost was measured.
It was a minute.

Comparative Example 3 Using an agglutination test tube not coated with a synthetic polymer,
When the blood coagulation time was measured by the same method as in Example 4, it was about 5 minutes.

Example 5 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 synthetic polymer obtained in Example 3 according to the following method. Two
A 40% sulfuric acid aqueous solution containing 40% potassium permanganate was circulated in a polyvinyl chloride tube for 1 hour, and then distilled water was flowed for 10 minutes to wash and dry the polychlorinated product having hydroxyl groups introduced on the inner surface. A vinyl tube was obtained. In a 99% ethanol solution containing 0.5% acetic acid aqueous solution, a solution prepared by dissolving the synthetic polymer obtained in Example 3 to a concentration of 5% was placed in a polyvinyl chloride tube having hydroxyl groups introduced on its inner surface. After circulating for 5 minutes at room temperature and drying at room temperature, heat treatment at 50 ° C for 1 hour
A polyvinyl chloride tube coated with a synthetic polymer was obtained. 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 . The polyvinyl chloride tube was cut to a length of 5 cm, and was embedded in a manner to replace a part of the rabbit abdominal aorta. One day later, the polyvinyl chloride tube embedded in the rabbit was taken out, fixed with glutaraldehyde, and then the tube inner surface was observed with an electron microscope.
Only a small amount of protein was attached.

Comparative Example 4 A vinyl chloride tube obtained by washing the inner surface of the tube with an ethanol solution was embedded in a rabbit in the same manner as in Example 5, 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.

Example 6 A polysulfone hollow fiber membrane having an inner diameter of 300 μm was 0.1 mm ²
Using the built-in blood component separation module, the blood contact site was coated with the synthetic polymer obtained in Example 2 according to the following method. A solution of the synthetic polymer obtained in Example 2 dissolved in a 95% ethanol solution to a concentration of 0.5% was circulated for 30 minutes at the blood contact site of the module, and dried at room temperature. Under the same conditions, an ethanol solution containing a synthetic polymer was circulated again, dried at room temperature, and then 1
By heat treatment at 00 ° C. for 30 minutes, a module in which the blood contact site was coated with a synthetic polymer was obtained. This module was connected to a blood circuit, and platelet-rich plasma obtained from citrate-added blood (platelet count of about 100,000 / μl) was flowed for about 10 minutes at a flow rate of 0.3 ml / min, and the platelet-rich plasma passed through the module. The number of platelets was measured. When the platelet count of the platelet-rich plasma that passed through only the blood circuit was blanked and the platelet recovery was determined, it was 95% or more.

Comparative Example 5 The blood contact site of the blood component separation module incorporating the porsulfone hollow fiber membrane was washed with an ethanol solution and dried, and then the platelet recovery rate was determined in the same manner as in Example 6. However, it was about 50%.

Example 7 A cover glass was used, and the cover glass was coated with the synthetic polymer obtained in Example 3 according to the following method. The synthetic polymer obtained in Example 3 was added to a 95% ethanol solution at 5%.
Cover the glass with a solution of 10% cover glass.
After soaking for 1 minute and drying at room temperature, a heat treatment was performed at 100 ° C. for 6 hours to obtain a cover glass covered with a synthetic polymer. When the amount of phosphorylcholine groups on the surface of the substrate was measured by X-ray elemental analysis, it was 5 × 10 ^-6 mol / cm
^{Was 2} . This cover glass is immersed in warm water at 50 ° C., taken out every 6 hours, dried, and then measured for infrared spectrum to determine the change in absorption near 1720 cm ⁻¹ derived from the carbonyl group of the methacrylic acid ester of the synthetic polymer. Tracked. It decreased gradually until 24 hours, then became almost constant, and it was confirmed that 80% or more of the synthetic polymer remained even after 48 hours, showing durability against hot water. Further, the cover glass soaked in warm water of 50 ° C. for 48 hours was placed in a polymethylmethacrylate petri dish having the inner surface coated with the synthetic polymer obtained in Example 3, and 30 ml of adult fresh blood was poured into it, and the temperature was set to 37 ° Gently shaken for 30 minutes. After that, the cover glass was taken out, washed with water, dried, and the surface of the cover glass was observed with an optical microscope.

Comparative Examples 6 and 7 A cover glass was prepared in the same manner as in Example 7, except that the copolymer obtained in Comparative Example 1 or Comparative Example 2 was used in place of the synthetic polymer obtained in Example 3. And the durability in warm water was examined. In either case, the absorption near 1720 cm ^-1 almost disappeared after 6 hours, and no absorption was observed after 24 hours. Further, the cover glass immersed in warm water at 50 ° C. for 24 hours was immersed in adult fresh blood in the same manner as in Example 7, and the surface of the cover glass was observed with an optical microscope. As a result, adhesion of fibrin was observed. Thus, in the case of a material coated with a copolymer that does not have a silane-containing monomer unit that produces a silanol group by hydrolysis, the copolymer is desorbed in a short time and blood compatibility does not last for a long time. I understand.

[0042]

EFFECTS OF THE INVENTION The synthetic polymer for medical materials of the present invention has excellent blood compatibility and is unlikely to cause thrombus even when contacted with blood. In addition, the medical material whose surface is coated with the synthetic polymer for medical materials does not easily release the synthetic polymer with excellent blood compatibility that is coated on the surface of the base material. Holds stable over a long period of time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuhiko Higaki 1-1239 Umeda, Kita-ku, Osaka Kuraray Co., Ltd.

Claims (2)

[Claims] 1. A phosphorylcholine group content of 5 to 90.
A synthetic polymer for medical materials, wherein the content of the silane-containing monomer unit that produces a silanol group by hydrolysis is 0.01 to 10 mol%. 2. A medical material in which the surface of a base material is coated with the synthetic polymer for medical material according to claim 1.