JPH02138342A - Aba-type block copolymer, its production, and its use - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in biocompatibility and compatibility with PVC by reacting a hydrophilic polymer having a reactive group on one end with a vinyl chloride polymer having reactive groups reactive therewith on both ends. CONSTITUTION:A block copolymer of A-B-A type (wherein A is a hydrophilic polymer; and B is a vinyl chloride polymer) is obtained by reacting a hydrophilic polymer, desirably an ethylene glycol polymer or a 2-hydroxyethyl methacrylate polymer having a reactive group on one end [e.g., a reaction product of polyethylene glycol monomethyl ether with methylenebis(4-phenyl isocyanate)], with a vinyl chloride polymer having groups reactive therewith on both ends (e.g., a PVC having hydroxyl groups on both ends, obtained by reacting PVC with O3 to convert both ends into carboxyl groups and reacting the product with lithium aluminum hydride).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a novel ABA-type block copolymer, a method for producing the same, a biocompatible medical material using the novel copolymer,
The present invention relates to medical devices, surface hydrophilic agents, hydrophilic vinyl chloride resins, surface hydrophilic vinyl chloride molded articles with horizontal writing, and molded articles that deform upon contact with water.

[Prior Art] Conventionally, many polymer materials have been used as materials for artificial organs and medical materials, but when they come into contact with living bodies, they inevitably cause the formation of blood clots and inflammatory reactions. A block copolymer in which two different types of hydrophilic and hydrophobic chains are incorporated into one molecule is known as a material with improved properties.

This copolymer has a microphase-separated structure in which hydrophilic and hydrophobic chains form microdomains at the level of molecular assembly, so it is thought to have hydrophilic and hydrophobic regions (domains). It is attracting attention as a medical polymer material due to its excellent compatibility.

A typical poly(2-hydroxyethyl methacrylate-polystyrene) copolymer consists of a hydrophilic poly-2-hydroxyethyl methacrylate chain and a hydrophobic polystyrene chain in one molecule. It has a chain and is being developed for various uses in the medical field such as catheters, but it has weak mechanical strength when dry and is difficult to mold, and when coated with polyvinyl chloride, Because of its poor compatibility with polyvinyl chloride, it is prone to cracking, and when bending stress is applied, the tllfi phenomenon is likely to occur, making it difficult to use.

Also, considering useful resin materials with hydrophilic surfaces,
Conventionally, vinyl chloride resins have been used as industrial materials, but their surfaces are extremely hydrophobic. For this reason, condensation occurs on the surface when used in a humid environment, reducing transparency, and when water is poured into a vinyl chloride resin container, air condenses on the surface and bubbles form. There is. In order to improve these drawbacks, surfaces are made hydrophilic by blending surfactants and hydrophilic compounds into vinyl chloride resins. However, such compounds have problems such as poor compatibility with vinyl chloride and dispersibility, and also problems such as elution of the compound over time, making it difficult to maintain hydrophilicity. Also,
This method cannot be applied to molded objects.There is also a method of coating the molded object to be used with a hydrophilic material, but this also has poor adhesion to vinyl chloride resin and has problems with peeling and durability. was what remained.

Furthermore, while it has conventionally been acceptable for resins and metals to continuously maintain their shape when molded, there are some uses where it is preferable for the shape to change between before and during use.

For example, when inserting a catheter into a blood vessel, it is useful to have a catheter that is initially straight and bends when it reaches a predetermined location. However, it is not possible to manufacture such catheters using conventional materials.

Shape-memory alloys and shape-memory materials can be used as materials to answer such applications! There are 61 fats, but these cause changes in shape due to temperature changes past the transition point, so the temperature change between before and during use is small.
There is a problem in that it cannot be used under conditions where there is no temperature change. In addition, with shape memory alloys, etc., once deformed by -degrees, they will not return to their original shape unless force is applied.

[Problems to be Solved by the Invention] The object of the present invention is to provide a novel ABA type block copolymer that solves the problems of the prior art and has excellent biocompatibility and is compatible with polyvinyl chloride. It provides a polymer. Another object of the present invention is to provide a method for producing a novel ABA block copolymer that is compatible with polyvinyl chloride. Furthermore, the present invention
The purpose is to provide new medical materials. A further object of the present invention is to provide a medical device having a biocompatible and strong coating coated with a novel ABA type block copolymer that is highly compatible with polyvinyl chloride.

Furthermore, in order to solve the poor hydrophilicity of polyvinyl chloride resins as explained above, the present invention provides -Installation A- from a hydrophilic polymer (A) and a vinyl chloride polymer (B). B
-Providing a hydrophilic agent with good adhesion to polyvinyl chloride, a hydrophilic vinyl chloride resin, and a vinyl chloride resin molding with a hydrophilic surface by producing the ABA block copolymer represented by A. It is something to do. Another object of the present invention is to provide a vinyl chloride resin molded product that has improved surface hydrophilicity by containing a hydrophilic agent at least on the surface.

A further object of the present invention is to provide a molded article that deforms upon contact with water, which solves the problems of the prior art deformable molded articles as explained above. That is, the present invention provides an ABA type block copolymer synthesized from a polyethylene glycol polymer (A) and a vinyl chloride polymer (B), which is represented by ABA, and a plastic material. It was discovered that molded products deform when they come into contact with water.

In 4A-B-A, - is, for example, a diester bond, a peptyl bond, or an ester bond via a compound having a diisocyaner group.

In the present invention and this specification, the term "vinyl chloride polymer" means a polymer whose main component is a vinyl chloride monomer.

[Structure of the Invention] [Means for Solving the Problems] The present invention provides a novel method represented by -A-B-A (A is a hydrophilic polymer, and B is a vinyl chloride polymer). It is a block copolymer. Further, in the present invention, it is preferable that the hydrophilic polymer is an ethylene glycol polymer. Furthermore, the present invention provides a general polymer A, characterized in that a hydrophilic polymer having a reactive group at one end and a vinyl chloride polymer having reactive groups at both ends are added and reacted in a solvent.
This is a method for producing a novel block copolymer represented by -B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer). Further, in the present invention, it is preferable that the hydrophilic polymer is an ethylene glycol polymer. Furthermore, the present invention provides -Installation A-B-A (A is a hydrophilic polymer, B
is a vinyl chloride polymer). Further, in the present invention, a biocompatible medical material containing a block copolymer in which the hydrophilic polymer is an ethylene glycol polymer is preferred. Furthermore, the present invention provides a novel block copolymer represented by -A-B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer) on at least the surface of a medical device. This is a medical device characterized by the fact that Further, in the present invention, it is preferable that the hydrophilic polymer is an ethylene glycol polymer for medical use. Further, the present invention provides - installation A-B-A (A
B is a hydrophilic polymer, and B is a vinyl chloride polymer. Furthermore, in the present invention,
A surface hydrophilic agent in which the above-mentioned hydrophilic polymer is an ethylene glycol polymer is preferred. In addition, a surface hydrophilizing agent in which the hydrophilic polymer is a 2-doi'J quinethyl methacrylate polymer is preferable.
This is a hydrophilic vinyl chloride type #I pilgrimage characterized by containing a novel block copolymer represented by A (A is a hydrophilic polymer and B is a vinyl chloride type polymer). Further, in the present invention, a hydrophilic vinyl chloride resin in which the hydrophilic polymer is an ethylene glycol polymer is preferred.

Further, in the present invention, a hydrophilic vinyl chloride resin in which the hydrophilic polymer is a 2-hydroxyethyl methacrylate polymer is preferred.

Furthermore, the present invention is characterized in that a novel block copolymer represented by the general formula A-B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer) is formed on at least the surface. This is a vinyl chloride resin molded product with a hydrophilic surface. Further, in the present invention, a surface hydrophilic vinyl chloride resin molded product in which the hydrophilic polymer is an ethylene glycol polymer is preferred. Further, in the present invention, the hydrophilic polymer has 2
-A surface-hydrophilic vinyl chloride resin molded product which is a polymer of human [1-xyethyl methacrylate] is preferred.

The present invention provides a novel block copolymer represented by -A-B-A (A is a hydrophilic polymer, B is a vinyl chloride polymer) and a plastic material. It is a molded product that deforms upon contact.

The present invention also comprises a novel block copolymer represented by -A-B-A (A is a hydrophilic polymer, B is a vinyl chloride polymer) and a plastic material. It is a molded product whose surface is partially covered with a water-containing or water-permeable material and deforms when it comes into contact with water.

[Function] According to the present invention, a polyvinyl chloride polymer is treated with ozone to obtain a polymer having carboxyl groups at both ends, and this polymer can be used as it is or by performing various reactions to react at both ends. A polyvinyl chloride polymer having a functional group is obtained. A new ABA block copolymer obtained by reacting this polymer with a hydrophilic polymer having a reactive group at one end has excellent biocompatibility such as antithrombotic and antiinflammatory properties. At the same time as having
It has been found that it has good adhesiveness and compatibility with polyvinyl chloride, and is very effective as a coating for medical materials or medical devices. Furthermore, according to the present invention, the novel block copolymer represented by -A-B-A (A is a hydrophilic polymer and B is a vinyl chloride-based polymer) is a vinyl chloride-based resin. It is used as a surface hydrophilic agent for vinyl chloride resins, has good compatibility with vinyl chloride resins, has good sustainability, and has been found to be effective in improving the hydrophilicity of vinyl chloride resins and molded products. It is.

Further, the water-contact deformable molded product of the present invention is a general polymer A-B-A (A is a hydrophilic polymer) synthesized from a polyethylene glycol polymer (A) and a vinyl chloride polymer (B), This is based on the discovery that molded products made from a new block copolymer (B is a vinyl chloride polymer) and a plastic material deform when they come into contact with water. The novel block copolymer of the invention represented by -Installation A-B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer) is a polyvinyl chloride polymer having reactive groups at both ends. It is synthesized from a hydrophilic polymer and a hydrophilic polymer having a reactive group at one end.

The polyvinyl chloride polymer having reactive groups at both ends used as a vinyl chloride chain for producing the novel ABA type block copolymer of the present invention is prepared by heating the polyvinyl chloride polymer in a solvent at a predetermined temperature. A polyvinyl chloride polymer with carboxyl groups at both ends is formed by ozone treatment, and then this is synthesized as is or by various reactions to introduce reactive groups. Ru.

The polyvinyl chloride polymers that react with ozone used in the present invention include not only polyvinyl chloride alone, but also polyvinyl chloride-vinyl acetate copolymers, polyvinyl chloride-ethylene-vinyl acetate copolymers, Polyvinyl chloride-vinylidene chloride copolymer and the like can be used. Average degree of polymerization 3
00 to 5000, preferably 600 to 1600. The organic solvent used is dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene,
Dichlorobenzene and the like are preferred.

These organic solvents contain 1 to 30% by weight of polyvinyl chloride,
The content is preferably adjusted to 3 to 10% by weight. 5 to 400 mg of ozone per minute, preferably 10 to 20 mg per minute
Passed into the polyvinyl chloride solution at a flow rate of 0 mg, 50-1
20-2 at a temperature of 80°C, preferably 60-100°C
00 hours, preferably 50 to 100 hours.

In order to recover the reactant from the reaction solution obtained by this ozone treatment, the reaction solution should be concentrated, or taken out from the reaction container as it is, or diluted with an organic solvent, and diluted approximately 10 to 50 times. The reaction product may be precipitated by adding the reaction product dropwise into a poor solvent such as methanol having a volume of 100 ml, followed by filtration, followed by drying.

The obtained polyvinyl chloride having carboxy groups at both ends was processed by vapor pressure osmosis method (Vapor Pressure O
sm.

The number average molecular weight measured by @6try > is approximately 100
0 to 60,000. (The number average molecular weights listed below are from the same measurement method).

The polyvinyl chloride polymer having carboxyl groups at both ends obtained in this way can be used as is for the next reaction with a hydrophilic polymer or polymer, or it can be further converted into other reactive groups by various reactions. You can also do that. Examples of the reactive groups used include, in addition to carboxyl groups, hydroxyl groups, acid chloride groups, active Nisder groups, incyanate groups, and the like.

The polymerization reaction between the obtained polyvinyl chloride polymer having reactive groups at both ends and the hydrophilic polymer having a reactive group at one end is carried out in a suitable solvent.

Organic solvents used according to the invention include ether,
Tetrahydrofuran and the like are used.

In these organic solvents, polyvinyl chloride having carboxyl groups at both ends is 0.5 to 10% by weight, preferably 2% by weight.
- 5% by weight, add a predetermined amount of the above-mentioned reactive base, and heat at 10 to 50°C, preferably 25 to 35°C.
The reaction is then carried out for 6 to 48 hours, preferably for 8 to 16 hours.

In order to recover the reactant from the reaction mixture that has been subjected to a polymer polymerization reaction in this way, the reaction solution can be concentrated, or it can be left as it is, or it can be diluted with an organic solvent and taken out from the reaction container and 10 to 20 times the volume. Any method can be used, such as dropping the reaction product dropwise into a poor solvent such as hexane to precipitate it, filtering it, and then drying it. The obtained block copolymer can be purified using a fractional precipitation method or a reprecipitation method.

The block copolymer thus obtained is: -Installation A
-B-A (A is a hydrophilic polymer, B is a vinyl chloride polymer). The other side A is hydrophilic and the other side B is hydrophobic. By changing the molecular weights of A and B, the hydrophilicity and hydrophobicity can be changed, thereby changing the state of assembly of the chains, and by selecting an appropriate solvent, the state of microphase separation can be controlled over a wide range. Can be done.

Such control of the microphase-separated structure cannot be achieved with blenders, and they exhibit good biocompatibility that homopolymers or random copolymers do not have.

Among the block copolymers of the present invention, the diisocyanates that can be used to produce the polyethylene glycol having an incyanato group at one end, denoted as A, include aromatic or aliphatic diisocyanates, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 1-tri-110-2.4-phenylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-)lylene diisocyanate, 3゜3゛-dimethyl-4,4°-biphenylene diisocyanate, 3.
3゛-dimethoxy-4,4゜biphenylene diisocyanate, 2,2゜,5゜5゜-tetramethyl-4,4′-
biphenylene diisocyaner], methylene bis(4-
phenyl isocyanate), methylene bis(2-methyl-4-phenylene isocyanate), methylene bis(4
-cyclohexyl isocyanate), etc. can be used.

In the addition reaction between polyethylene glycol having a hydroxyl group at one end and the above-mentioned diisocyanates, the polymer concentration should be adjusted to 5 to 40% by weight in an organic solvent, or the polymer should be heated above the melting point of the polyethylene glycol without a solvent. The functional group ratio of incyanate groups to aqueous groups is adjusted to about 2:1, and the temperature is 60 to 150°C, preferably 80 to 100°C, for 1 to 12 hours, preferably 2 to 100°C. It will be held for 6 hours. Examples of organic solvents include benzene, toluene, di[10benzene, N,N dimethylformamide, tetra5F1.1furan, dioxane, dichloroethane, trichloroethane, tetracI]ruethane, and the like.

The block copolymer of the present invention thus obtained is transparent, and can be dissolved in a solvent, cast or molded into any shape such as a film, plate, or tube, and then removed by removing the solvent, or It can be molded by heating and melting, and can be applied to artificial blood vessels, artificial skin, catheters, etc. The block copolymers of the present invention can also be used as a separate component to coat the surface of a medical device.

In the present invention, the ratio of functional groups of isocyanate groups and hydroxyl groups is determined by using a reaction mixture of the polyethylene glycol and a catalyst in a solvent such as dimethylformamide, detrahydrofuran, dioxane, etc. or without using a catalyst. , mixed in a ratio of about 1=1, adjusting the polymer concentration to 1 to 20% by weight, and heating at 60 to 120°C, preferably 80 to 10%.
The reaction is allowed to proceed at a temperature of 0°C for 2 to 40 hours, preferably 4 to 20 hours.

In order to take out the reaction mixture from the reaction mixture that has been subjected to a polymerization reaction in this way, the reaction mixture must be concentrated, or taken out from the reaction vessel as it is, or diluted with an organic solvent and 10 to 50 times more concentrated. Any method can be used, such as dropping the reaction product dropwise into a poor solvent such as hexane to precipitate it, filtering it out, and drying it. The obtained block copolymer can be purified using a fractional precipitation or reprecipitation method.

In this case, the fractional precipitation method utilizes the difference in temperature dependence of solubility between two types of prepolymers and a block copolymer. The reprecipitation method is a method in which reprecipitation operations are repeated in a solvent in which each prepolymer is soluble and the block copolymer is insoluble.

In the isocyanate block copolymer thus obtained, the A-B-A block copolymer has the general formula % (wherein X1 is R"-0-(CHm-CHm- 0-)-[
In the formula, R1 is a hydrocarbon or acyl group having 1 to 20 prime numbers, and n represents an integer of 10 to 500: lxl
teeth.

-co, -co-co, -cH, - [where m is 15-5
00 integer 1-], R' is a residue of diisocyanate).

Among these, xl is hydrophilic, xl is hydrophobic, and x
By arbitrarily selecting the molecular weights of l and x2, hydrophilicity,
Change the hydrophobicity and thereby control the assembly state of the chain 1
- It is possible to control the microphase separation structure over a wide range by selecting an appropriate solvent.

Such control of the microphase-separated structure cannot be achieved with blenders, and the surface having the microphase-separated structure exhibits good biocompatibility that homopolymers or random copolymers do not have.

This plastic copolymer is transparent and can be molded by dissolving it in a solvent, casting it into any shape such as a film, plate, or tube, and removing the solvent, or by heating and melting it. It can be applied to artificial blood vessels, artificial skin, catheters, etc. It can also be used as a separate component to coat the surface of a medical device.

Regarding the production of the novel ABA type block copolymer of the present invention described above, the hydrophilic region and the hydrophobic region can be arbitrarily selected and designed. That is, the chain length of polyvinyl chloride having hydroxyl groups at both ends is determined by selecting the molecular weight of polyethylene glycol having a hydroxyl group at one end by reprecipitation method or fractional precipitation method, and these operations are as follows: It is easy and convenient.

Further, the bond between the hydrophobic chain and the hydrophilic chain is caused by a reaction between both ends of the polyvinyl chloride polymer and a reactive group at one end of the hydrophilic polymer.

By selecting this reactive group, the reaction conditions can also be selected. A block copolymer having both hydrophobic chains and hydrophilic chains is produced by the reaction between the reactive groups, and a block copolymer having a clear molecular structure and desired properties can be produced.

According to the production method of the present invention, molecular weight, molecular chain length, and molecular chain length ratio can be obtained as designed.

Therefore, compared to conventional polymers having hydrophilicity and hydrophobicity, the block copolymer of the present invention can form hydrophilic and hydrophobic regions at the molecular assembly level, and is therefore biocompatible. This makes it possible to effectively use it as a plastic material.

According to the present invention, a novel block copolymer represented by -A-B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer) can be used to hydrophilize the surface of a vinyl chloride resin. It can be used as an agent and has good compatibility with vinyl chloride resin.
It has good sustainability and is useful for improving the hydrophilicity of vinyl chloride resins and molded products.The hydrophilic polymers used in the surface hydrophilizing agent for vinyl chloride resins according to the present invention include: , ethylene glyfur, 2-hydroxyethyl methacrylate, vinyl alcohol, N-vinylpyrrolidone, acrylamide, etc., preferably,
Polymers of ethylene glycol and 2-hydroxy methacrylate are used.

The novel octapolymer of the present invention represented by -A-B-A (A is a hydrophilic polymer and B is a vinyl chloride polymer) has reactive groups at both ends. It is synthesized from a polyvinyl chloride polymer and a hydrophilic polymer having a reactive group at one end.

The block copolymer synthesized in this way is transparent and can be coated on molded articles by dissolving it in an appropriate solvent.6 Examples of solvents used in the surface hydrophilizing agent of the present invention include acetone, chloroform, , dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, tetrahydrofuran, etc.

Further, the block copolymer of the present invention can be heated and dissolved, and then coated on a vinyl chloride resin molded article to make the surface hydrophilic. It can also be added directly to the vinyl chloride resin. The polyvinyl chloride resin containing this hydrophilic agent can be molded by conventional methods, and a molded product surface with good hydrophilic properties can be obtained.

In the A-B-A type block copolymer used in the hydrophilizing agent of the present invention, A is hydrophilic and B is hydrophobic, and the molecular weight, molecular chain length, and molecular chain length ratio of A and B are selected. By doing so, the degree of hydrophilicity can be adjusted.

The surface of a molded product treated with the hydrophilic agent of the present invention or the surface of a molded product molded with the hydrophilic agent of the present invention impairs transparency compared to the surface of an untreated vinyl chloride resin. It is possible to improve hydrophilicity without causing any damage, has good water wettability, and has excellent drip-proof and anti-fog properties. In addition, the hydrophilic agent does not elute even after long-term use, resulting in excellent sustainability. Furthermore, since it does not dissolve when it comes into contact with water, it can be used for food and medical purposes.

Furthermore, since the coating formed on the molded product has good adhesion to the vinyl chloride resin and has strong mechanical strength, peeling does not occur even when mechanical stress is applied.

Furthermore, according to the present invention, the vinyl chloride resin has non-eluting,
It is easy to impart long-lasting hydrophilicity, and it becomes possible to produce vinyl chloride resin molded articles with surface hydrophilicity.

Furthermore, the novel block copolymer represented by A-B-A (A is an ethylene glycol polymer and B is a vinyl chloride polymer) according to the present invention can be dissolved in a solvent and formed into any shape. It can be manufactured as a molded article by casting it into a mold and removing the solvent, or by heating and melting it and combining it with a plastic material. Moreover, it can also be molded by methods such as coating or heating melting on the surface of an already completed molded product. The flexible material to be used is not limited to resin, but may also include fibers, paper, inorganic materials, metals, etc., but from the viewpoint of adhesiveness, polyvinyl chloride resin is preferable.

Furthermore, according to the present invention, a molded article formed from an ABA type block copolymer and a plastic material can be deformed and hardened by contact with water. The rate of deformation is very rapid (and this deformation is reversible; by returning it to a water-free environment, it can be restored to its original shape and used again and again. Also, unlike shape memory alloys, If it comes into contact with water, the molded product of the present invention will deform even if there is no temperature difference.

The principle of this deformation is believed to be as follows.The A-B-A type block copolymer of the present invention is water-containing and swells when it contains water.

For this reason, the degree of swelling is different from that of the plastic material used when producing the water-contact deformable molded product of the present invention, causing deformation.The plastic material used in the water-contact deformable molded product of the present invention contains water. The block copolymers of the present invention, whether or not, harden and retain their deformed shape upon contact with water. This is thought to be because the polyethylene glycol chain used in the block copolymer of the present invention specifically binds to water, and water acts as a restraining agent. General water-containing 411J11 also swells when it comes into contact with water, but the water content causes it to become molar, and does not harden, making it impossible to obtain the effects of the present invention.

Furthermore, the rate of deformation in the water-contact deformable molded product according to the present invention depends on the molecular weight, molecular chain length, and molecular chain length ratio of the polyvinyl chloride chain and polyethylene glyfur chain of the A-B-A type block copolymer. Preferably, the content of ethylene glycol is 40 to 40%, although it can be varied.
60 mol%, the molecular weight of the ethylene glycol polymer is 1
, Go.

~to, ooo are used. It can also be changed depending on the plastic materials used in combination.

In addition, by covering the surface of the water-contact deformable molded product according to the present invention with a water-containing or water-permeable material and changing the type, thickness, and area of this material, it is possible to Arbitrarily change the time from to transformation 1 #i4#! I can.

Application examples of the molded product of the present invention that deforms when it comes in contact with water include, for example, a vascular catheter whose tip bends when placed in blood and can be easily inserted into a curved blood vessel, and a catheter that can be inserted into a blood vessel or the abdominal cavity. Vascular catheters, indwelling needles, and CAPDs whose tips can be bent or expanded to prevent detachment.
Examples include catheters for use.

Next, the present invention will be explained using specific examples, but the present invention is not limited by the explanations.

[Example 1] [Production of polyvinyl chloride having carboxyl groups at both ends] Polymer C: 35 g of polyvinyl chloride having a number average molecular weight of 60,000 was dissolved in 400 ml of dichloroethane, and while ozone was flowing at 17 mg/min into the solution. After the reaction was completed at 70° C. for 400 hours, analysis revealed that a polymer having a number average molecular weight of 8.000 and having an average of 1.9 carboxyl groups per molecule was obtained.

Polymer B: The same reaction as in the production of Polymer A was carried out, except that the reaction time was 100 hours. A polymer with a number of carboxyl groups in one molecule of 1.95 and a number average molecular weight of 3300 is 80
% reaction rate was obtained.

Polymer C: 100 g of polyvinyl chloride having a number average molecular weight of 100,000 was dissolved in 21 ml of tetrachloroethane, and a reaction was carried out by flowing ozone at 200 mg/min at 70° C. for 30 hours. A polymer having a number of carboxyl groups per molecule of 1.8 and a number average molecular weight of 3,700 was obtained at a reaction rate of 85%.

Polymer C: 100 g of polyvinyl chloride with a number average molecular weight of 40,000 was dissolved in 1 l of dichloroethane, and ozone was added at 1/min.
The reaction was continued at 20 mg at 70° C. for 50 hours. Number of carboxyl groups in one molecule is 1.7, number average molecular weight 430
0 polymer was obtained with a reaction rate of 75%.

Polymer E: 10 g of Polymer A was added to tetrahydrofuran (T
A solution of 0.7 g of lithium aluminum hydride suspended in 150 mH of THF was added to a solution dissolved in 220 milliliters of HF) and reacted at 25°C for 12 hours. After concentrating the reaction solution, it was diluted 20 times as a reprecipitation solvent. Purification using a volume of methanol. number average molecule is o o
o polymer was obtained with a reaction rate of 90%.

Polymer F: Polymer B was used in the same reaction as Polymer E. Botsumer with number average molecular weight 3300 is 95
% reaction rate was obtained.

Polymer G: The reaction was carried out in the same manner as Polymer E using Polymer C. Bommer with number average molecule ff3700 is 9
A reaction rate of 5% was obtained.

Polymer H: Using Polymer D, the reaction was carried out in the same manner as Polymer E. Bommer with number average molecular weight 4300 is 93
% reaction rate was obtained.

Polymer■: 100 g of polyethylene glycol monomethyl ether and methylene bis(
4-phenylisocyanate) was dissolved in 1 liter of N,N-dimethylformamide at 100°C.
After the reaction was completed for 0 hours, analysis revealed that a polymer with a number average molecular weight of 2300 and an average of 0.96 incyanato groups per molecule was obtained.

Polymer J: 100 g of polyethylene glycol monomethyl ether with a number average molecular weight of 5000 and methylene bis(4
-phenylisocyanate) was dissolved in N,N-dimethylformamide IJ-methol and reacted in the same manner as Polymer (1). A polymer having 0.99 incyanato groups per molecule and a number average molecular weight ff of 15,300 was obtained with a reaction rate of 100%.

The polymer was reacted in the same manner except that 8.85 g of 2,4-1-lyene diisocyanate was used in place of methylene bis(4-7 enyl isocyanate) in Polymer (1). The number of incyanato groups in one molecule was approximately 1, and a polymer having a number average molecular weight of 2200 was oxidized with a reaction rate of 98%.

Polymer L: The reaction was carried out using Polymer ①, except that N,N-dimethylformamide was not used, and the other conditions were the same. Number average molecular r&230 with 0.96 isocyanate groups in one molecule
0 polymer was obtained with a reaction rate of 100%.

3% by weight N,N-dimethylner-11 amide solution 1
00ml and Polymer E(7) concentration is 11.3% by weight N,N-dimebourne! -lumamide solution 1
80ml was added and reacted at 80°C for 200 hours.The ratio of incyanate groups to hydroxyl groups before the reaction was approximately 1.
The reaction solution after the completion of the 0 reaction adjusted to be
, N-dimethylformamide, taken out from the reaction vessel, and added dropwise to 20 times the volume of ether to precipitate the reaction mixture, filtered and dried to recover the reaction mixture.

Add this reaction mixture to methanol and add the insoluble Bommer E.
and the block copolymer are separated by filtration, then dried, and further,
Add this reaction mixture to chloroform, filter the soluble part,
Dropped into 20 times the volume of hexane, filtered and dried. By repeating the above steps twice, the number average molecule ff112,5 was obtained.
A block copolymer of No. 00 was obtained in a yield of 60%.

Block co-merger B; 8.3 mg of tin dibutyl dilaurate and 17 mg of triethylene diamine were added as a catalyst,
The reaction time was 12 hours, and the others were P-J yy copolymer A.
I did the same thing. A block copolymer having a number average molecular weight of 12,500 was obtained in a yield of 73%.

Pr17 Ri゛ (combined C-F.

Using the polymers, concentrations, and amounts of solutions shown in Table 1, the reaction was carried out under the same reaction conditions as in the production of block copolymer A, and purification was performed.

Table 2 shows the number average molecular weight of the obtained block copolymer,
The figure shows the yield.

The infrared absorption spectrum of the P1cock copolymer F of the blank example was measured using the KBr method using a model 295 infrared spectrometer needle manufactured by Hitachi, Ltd. The obtained measurement spectrum is shown in Figure 1. N-H stretching vibration originating from the urethane bond was detected at #3420 cam-' and C-O stretching vibration originating from the urethane bond was detected at 1720 cm-'.
C- derived from polyethylene glycol chain at 0 cm-'
O stretching vibration is shown at 620c+a-', and C-C1 stretching vibration derived from polyvinyl chloride chain is shown at 620c+a-'.* 2910 Cra
-', 2870 cm-' shows C-H stretching vibrations derived from polyvinyl chloride chains and polyethylene glycol chains.

[Example 2] Polymer A1: Polyvinyl chloride 5 with an average degree of polymerization of 1000
0g was dissolved in 1000ml of dichloroethane and heated at 70°C while flowing 17mg of ozone into the solution per minute.
The reaction was carried out for 300 hours at a temperature of 0.0, and analysis after the completion of the reaction revealed that a polymer having an average number of 1.9 carboxyl groups per molecule and a number average molecular weight of 9,100 was obtained.

Polymer B1: The same reaction as Polymer A1 was carried out except that the reaction time was 50 hours. The average number of carboxyl groups in one molecule is 1.95, and the number average molecular weight is 6000.
% reaction rate was obtained.

[Production of polyvinyl chloride-based composite with reactivity at both ends] In a solution of polymer C1 and polymer At (40 g) dissolved in 890 milliliters of tetra-L dolphuran (THF), 2°88 of lithium aluminum hydride was added to THF605.
A milliliter of the suspended solution was added and reacted at 25°C for 12 hours, and the 0 reaction solution in which carboxyl groups were reduced to hydroxyl groups was concentrated, and then purified using 20 times the volume of methanol as a reprecipitation solvent. A polymer having a number average molecular weight of 9100.1 and 1.8 hydroxyl groups per molecule was quantitatively obtained.

Polymer D1. Polymer Bl (30g) in THF300
Add 50 ml of thionyl chloride and 1 ml of N,N-dimethylformamide (DMF) and react at 60°C for 48 hours. After evaporating the reaction solution to dryness, dissolve it again in 300 ml of THF and reprecipitate. Purification was performed using 20 times the amount of hexane as a solvent. It has a number average molecular weight of 6000, with 1.
A polymer having eight acid [1-J groups] was quantitatively obtained.

Polymer E1: Polymer Di (10g) was converted into N-methyl-
Dissolved in 100 ml of 2-pyrrolidone (NMP), added 1 g of 1-human Uxybenzotriazole and 0.5 ml of propylene oxide, and reacted at room temperature for 3 hours. Then, 20 times the amount of hexane was used as a reprecipitation solvent. Purified. A polymer having a number average molecular weight of 6300 and 1.7 1-benzotriazolyl ester groups in one molecule was obtained with a yield of 95%.

[Production of an aqueous polymer with a reverse reaction at one end] Polymer F1: 100 g of polyethylene glycol monomethyl ether with a number average molecular weight of 2000 and methylene bis(4-
(phenylisocyanate) 5゜08g dioxane 1,
After the reaction, the number average molecular weight was 2300, with an average of 0.96 incyanato groups per molecule.
of polymer was obtained.

Polymer G1; 2-hydroxyethyl methacrylate 6
0g, 2-aminoethanethiol 18g1 azobisisobutyronitrile (AIBN) 0.15g DMF120
The reaction solution, which was dissolved in 50 g and reacted at 60°C for 5 hours, was poured into 20 times as much ether and repeated for reprecipitation and purification. Number average molecule [6300, 0.9 amino groups in one molecule
A boJmer having 5 molecules was obtained with a yield of 90%.

Add 100 milliliters of a dioxane solution in which the concentration of the polymer F1 is 11.3% by weight and 200 milliliters of a dioxane solution in which the concentration of the polymer C1 is 11.3% by weight, and then heat the mixture at 100℃ for 20 hours. The ratio of the reactive groups before the reaction was adjusted to 1:1.The reaction solution after the completion of the reaction was diluted with dioxane, taken out from the reaction solution, and added dropwise to 20 times the amount of ether to react. After the mixture was precipitated, it was filtered and dried to recover the reaction mixture.

This reaction mixture was added to methanol and the insoluble bomer was added to
1 and the block copolymer were separated by filtration, then dried, the reaction mixture was added to chloroform, the soluble portion was filtered out, and the soluble portion was added dropwise to about 20 times the hexane volume, and the procedure of 6 or more was performed by filtering and drying. By turning green twice, the number average molecular weight is 13,700.
A block copolymer of 60% was obtained.

Pro/recopolymer B1: 10 g of polyethylene glycol monomethyl ester with a number average molecular weight of 5000 and polymer Di (6 g) were dissolved in 320 ml of NMP, 1 ml of triethylamine was added, and
After the reaction was completed, the reaction solution was diluted with NMP, taken out from the reaction solution, and added dropwise to 20 times the volume of ether. After the reaction mixture was precipitated, it was filtered and dried. It was purified in the same manner as Polymer A1. A block copolymer with a number average molecular weight of 1i16000 is 65
% yield.

Block copolymer C1: Polymer Gl (10 g) and polymer Di (5 g) were dissolved in 320 ml of NMP, 1 ml of triethylamine was added, and the mixture was heated to 80°C.
After the reaction was completed for 0 hours, the reaction solution was diluted with NMP, taken out from the reaction vessel, and added dropwise to 20 times the volume of ether to precipitate the reaction mixture, and then filtered and dried to recover the reaction mixture. It was purified in the same manner as the 1-block copolymer A1. A block copolymer having a number average molecular weight of 18,000 was obtained in a yield of 70%.

Puri rJ/Rikyo combination D1: Bori? -El (10 g) and polymer Gl (20 g) were dissolved in 320 ml of NMP and reacted at 0°C for 8 hours.

After completion of the reaction, the reaction solution was diluted with NMP, taken out from the reaction vessel, and added dropwise to 20 times the amount of ether to precipitate the reaction mixture, filtered and dried to recover the reaction mixture, and block copolymer A1 It was purified in the same manner. A block copolymer having a number average molecular weight of 18,000 was obtained in a yield of 63%.

The number average molecular weight and yield of the obtained block copolymer were
Shown in the table.

Entering Yu 1 Pu o Tsuku Copolymer AI BI CI
Di yield (%) 60 65 70 63
Number average molecular weight 13700 16000 18000
The infrared absorption spectrum of the block copolymer A1 of Example 18000 was measured using the KBr method using the Hitachi manufactured top 295.
It was measured by a model infrared spectrophotometer. The measurement spectrum obtained as a result is shown in Figure 2. At 3420 cm-', the absorption due to N-H stretching vibration originating from the urethane bond is 1
Absorption due to C-0 stretching vibration originating from urethane bond is detected at 720ea+-', and absorption due to C-C stretching vibration originating from polyethylene glycol chain is detected at 1110 cm-'. It shows absorption due to C-H stretching vibration derived from polyethylene glycol chain.

[Example 3] A polyvinyl chloride tube (inner diameter 1.4 mm, length 20 cm) was coated with a solution in which the ABA-type plastic copolymer A produced in Example 2 above was dissolved in dichloroethane, and rabbit veins were coated. After injecting a predetermined amount of freshly collected blood and connecting the polyvinyl chloride tube with a silicone tube, the tube is rotated at a predetermined number of rotations using a rotation device to determine the time it takes for a thrombus to form in the tube and the chamber to close. It was measured. Compared to uncoated, untreated polyvinyl chloride, tubes coated with the block copolymer were found to take 3-5 times longer to close. Manufactured At, Bl, CI, D
It can be seen that the block copolymer of the present invention, which showed similar results to the AHA type block copolymer of I, has excellent biocompatibility.

In addition, these block copolymers have been tested in accordance with the Japanese Pharmacopoeia's plastic container testing methods for infusions, including heavy metal tests, leachables tests, acute toxicity tests, sarcastic reaction tests, pyrogen tests, hemolytic tests, and transplantation tests. I did it and everything passed.

Also, when stress such as bending is applied to a member coated with polyvinyl chloride with these block copolymers,
No peeling or cracking was observed, indicating good adhesion and mechanical properties.

All the ABA type pro/recopolymers produced in Example 2 showed similar results.

[Example 4] ABA type block copolymer A produced in Example 2 above
A polyvinyl chloride tube (inner diameter 1.4 mm, length 20 crn) was coated with a solution of 1 dissolved in dichloroethane, a predetermined amount of fresh blood collected from a rabbit vein was injected, and the polyvinyl chloride tube was coated with a silicone tube. After connecting with a tube, the tube was rotated at a predetermined number of rotations using a rotation device, and the time until a thrombus was formed in the tube and the chamber was closed was measured. Compared to uncoated, untreated polyvinyl chloride, block copolymer coated tubes were found to have a 3-5 times longer time to closure. All the ABA type block copolymers produced in Example 2 showed similar results, indicating that the block copolymers of the present invention have excellent biocompatibility.

In addition, these block copolymers were subjected to heavy metal tests, leachate tests, acute toxicity tests, sarcastic reaction tests, pyrogen tests, hemolysis tests, and transplant tests in accordance with the Japanese Pharmacopoeia's plastic container test methods for infusions. All in all, I passed.

Also, when stress such as bending is applied to a member coated with polyvinyl chloride with these block copolymers,
No peeling or cracking was observed, indicating good adhesion and mechanical properties.

All the ABA type block copolymers produced in Example 2 showed similar results.

[Example 5] Production of biocompatible material A stainless steel wire with a diameter of 1.4 mm was repeatedly coated with a solution of block copolymer C-F dissolved in N,N-dimethylformamide to form a stainless steel wire with an inner diameter of 1.4 m and an outer diameter of 1.4 m. A tube with a length of 2.0 m and a length of 100 ann was produced. These tubes can be used as materials for vascular force i.-chill.

Regarding the antithrombotic properties of these materials, eight tubes cut into 20 Cffll lengths were cut using the Chandler loop method (Chandler, AB).
, A., B.]; In vitro method for brochures;
itro tbrombotic coagulati
on of the blood-A method
for producing a throa+bus
], Laboratory Investment [Lab, Inv
est, ]7:110-114.1958), the time until book closing was measured and investigated. The results are shown in Table 4.

Coagulation time (relative value with polyvinyl chloride tube as 1) Copolymer C3, B ± 0.8 Copolymer D 3.6 ± 0.7 Copolymer E 3.9 ± 0.4 Copolymer Coalescence F 3.9±1.2 [Example 6 Preparation of biocompatible material'1 A solution of block copolymers A1 to D1 dissolved in dichloroethane was repeatedly coated on a stainless steel wire with a diameter of 1.4 mm. Inner diameter 1.411 outer diameter 2.0m
A tube with W11 and a length of 100 cITl was prepared. These tubes can be used as materials for vascular catheters.

Regarding the antithrombotic properties of these materials, eight of the above tubes cut into lengths of 20CI11 were tested using the Chandra loop method (Chandtar, A.B.).
Author: A, B, ] In Vitro Pick Coagulation Method
Forepu ``1 Juusing a 'nronba;z, [
In vitro throIIIbotic coa
gulation of the blood-Am
method for producing a thr
ombus], Laboratory Investment [Lab
, Invest, ] 7:110-114, 1958), the time until room closing was measured and investigated.

The results are shown in Table 5.

TurtleΣλ Block copolymer A1 Block copolymer B1 Block copolymer C1 Block copolymer D1 Coagulation time (relative value with polyvinyl chloride tube as 1) 3.2±0.8 3.3±0.8 3 .0±0.7 3.1±1.2 [Example 7] [Biocompatibility test of medical materials according to the present invention] The ABA type block copolymer used in Example 4 was mixed with N,N-dimethyl A transparent film was produced by casting a solution dissolved in formamide on a glass plate and removing the solvent by vacuum drying.This film was cut into 81 square pieces, and a 3.8% sodium citrate solution (1 Nine volumes of blood were collected from a person using a syringe containing 9 volumes of blood, and a fixed amount of platelet-rich plasma obtained by centrifugation was placed on top of the blood and incubated at room temperature for a predetermined period of time. After lightly washing with saline and fixing with 2.5% glutaraldehyde solution, the block copolymer had a smaller number of adherent platelets and almost no deformation of the platelets when compared with the case of general polyvinyl chloride resin using SEM. It was revealed that the block copolymer according to the present invention, which was not obtained, is an excellent biocompatible material.

The block copolymers A1 to D1 of Example 2 were
A transparent film was produced by casting a solution dissolved in U ethane onto a glass plate and removing the solvent by vacuum drying. This film was cut into 8ff1 squares, 3.8% sodium citrate solution (1 volume) was poured on top of the film, 9 volumes of blood was collected from a person using a syringe, and platelet-rich blood was obtained by centrifugation. Plasma was incubated at room temperature for a specified period of time. After washing thoroughly with physiological saline containing sodium citrate and fixing with 2.5% glutaraldehyde solution, SEM shows that the block copolymer of the present invention was compared with that of a general polyvinyl chloride resin. In the obtained film, the number of adherent platelets was small, and almost no deformation of platelets was observed.The block copolymer according to the present invention was found to be an excellent biocompatible material.

[Example 8] [Biocompatibility test of medical materials according to the present invention] Coat glass beads with a solution of block copolymer A1 produced in Example 2 dissolved in dichloroethane - Serum separated from blood collected from a person The tube was placed in a container and incubated at 37° C. for 30 minutes. The complement value (CH2O) of this serum was measured by the 50% hemolysis method. Even when compared with serum that has not been in contact with anything, almost no complement activity was observed, demonstrating that the block copolymer of the present invention has excellent biocompatibility in terms of complement activity as well. .

[Example 9] [Manufacture of jjl aqueous vinyl chloride resin] KHA; a vinyl chloride polymer with a number average molecular weight of 60,000 and hydroxyl groups at both ends;
An ABA type block copolymer was synthesized from polyethylene glycol having a number average molecular weight of 1i1525Q and an isocyanate group at one end. Sample A was obtained by coating a polyvinyl chloride sheet with the above block copolymer dissolved in dichloroethane at a concentration of 4% and drying.

X-Dan B: The block copolymer synthesized in Sample A was placed on a vinyl chloride sheet, and the weight was 400 kg/cm at 100°C.
Press molding was carried out for 1 minute at a pressure of .

Human engineering: Sample A of the block copolymer C1 of Example 2
Coated in the same way.

Kaoru Hoshi: One drop of distilled water was dropped on the untreated vinyl chloride sheet and Samples A, B, and C, and the contact angle was measured using a spectacular contact angle measuring device manufactured by Elma Optical Co., Ltd.

The results are shown in Table 6. It was clearly seen that the surface hydrophilicity of all samples 1-0 was improved by the hydrophilic agent.

In addition, these samples were subjected to [] heavy metal test, leachate test, acute retest, sarcastic reaction test, pyrogenic substance test, hemolysis test, according to the infusion plastic container test method of this pharmacopoeia.
It was revealed that he passed the transplant test.

Untreated vinyl chloride sheet 92 degrees [Example 10] [1 Ml aqueous vinyl chloride molding] Samples A and B of Example 9 and an untreated vinyl chloride sheet were placed at room temperature in a container with 100% humidity. When placed, many water droplets adhered to the untreated PVC sheet, while
In samples A and B, uniformly wet water droplets were not observed. 6
Similar results were obtained for the sample after being left for several months, clearly demonstrating its excellent sustainability.

[Example 11] [Hydrophilized molded product 2 according to the present invention] 50 parts by weight of the block copolymer used in Sample A of Example 9 was blended with 100 parts by weight of polyvinyl chloride, and 1
Pressure was applied at 70°C and 400 kg/cm'' for 3 minutes to form a sheet-like molded product.The contact angle of the sample was measured in the same manner as in Example 9, and it was found that the hydrophilic molded product produced in this example The wet contact angle of the sheet was 56 degrees, while the contact angle of the untreated vinyl chloride sheet was 92 degrees.

[Example 12] [Surface hydrophilicity of molded product according to the present invention] A polyvinyl chloride infusion circuit was coated with a 4% dichloroethane solution of the block copolymer used in Sample A of Example 9, and dried. . Physiological saline in a soft bag was flowed at the same flow rate using the untreated infusion circuit and the coated circuit. In the case of the untreated infusion circuit, air bubbles adhered to the tube within the circuit, whereas in the coated circuit, there were no air bubbles and dripping was possible smoothly.

[Example 13] [Molded article 1 that deforms upon contact with water] Number of molecules homogeneous 16
Polyvinyl chloride having a hydroxyl group at both ends of 000 and polyethylene glycol having an incyanate group at one end and having a number average molecular weight of 2250 were reacted in dioxane at 100°C for 24 hours to form an A-B-A type polymer. A copolymer was synthesized.

Polychlorinated beer 100ffifa club and DOP5o! II
The above block copolymer was heated at 100°C on a polyvinyl chloride sheet with a thickness of 1 m, called Tokara, at a weight of 400 kg/
A pressure of c+a'' was applied and pressed for 1 minute to create a two-layer sheet as shown in Figure 3A. In Figure 6, 1 is the block copolymer of the present invention and 2 is polyvinyl chloride. be.

This sheet has a straight shape when dry.

When this sheet was soaked in distilled water at room temperature and temperature, it immediately deformed into the shape shown in No. 3 fiB.

Thereafter, when it was taken out of the water and left in the air, it recovered to its original shape as shown in FIG. 3A.The above operations were repeated five times, but the same deformation and recovery occurred.

[Example 14] [Molded article 2 that deforms upon contact with water] The surface of the two-layered Pro-7 copolymer sheet used in Example 13 was coated with poly2-
A sheet as shown in FIG. 4 was prepared by coating with a 4% methanol solution of hydroxyethyl methacrylate. 1 is a block copolymer, 2 is polyvinyl chloride, and 3 is poly 2-e droxyethyl methacrylate. When this sheet was immersed in distilled water as in Example 13, deformation occurred 20 seconds after immersion.

[Example] 5] [Molded article 3 that deforms upon contact with water] The inside of the tip of a vinyl chloride catheter was coated with a 6% solution of dichloroethane using the same pro-copolymer used in Example 13. In Figure 0, a catheter as shown in Figure 5A was prepared, 1 is a block copolymer, and 2 is polyvinyl chloride. Insert this catheter into the rabbit's abdominal cavity, and
PD peritoneal perfusion was performed. The size of the incision when inserting the catheter is small, and even if you pull the catheter, it will not come out.
, which was effective in preventing falling off. That is, after insertion,
The catheter made according to the present invention is the 5th cgJB
It is deformed as shown in Figure 2, and has the remarkable effects mentioned above.

[Example 16] [Molded article for guide wear according to the present invention] A molded product according to the present invention was prepared from internally polymerized vinyl chloride and a block copolymer.
In the figure, 1 is the block copolymer of the present invention, and 2 is vinyl chloride. Using this wire molding, a catheter was inserted from the femoral artery of a rabbit to the heart.The characteristics obtained by the present invention improve operability due to the deformation characteristics due to water contact, making it easier to insert the guide wire. Ta.

[Example 17] [Molded product for catheter according to the present invention] A tube as shown in FIG. 7 was produced according to the present invention from internally plasticized vinyl chloride and a block copolymer. It is a combination, and 2 is PVC! - It is le. The tip of this molded product bends 4' when placed in water.

[Effects of the Invention] The present invention has the following remarkable technical effects.

The novel ABA type block co-compensation aggregation of the present invention is, firstly,
By using a polyvinyl chloride polymer and a hydrophilic polymer, it has good compatibility with the polyvinyl chloride resin and excellent mechanical properties, and at the same time, the MIG11 phase between the hydrophilic region and the hydrophobic region A kjN-based P[knock copolymer is obtained by separating the KjN-based phenolic copolymer, which has excellent biocompatibility.

The method for producing the novel ABA type block copolymer of the present invention allows the molecular weight, molecular chain length, and molecular chain length ratio to be freely controlled by a convenient and easy-to-operate method, and the hydrophilic region and hydrophobic region can be freely controlled. It is determined by the chain length of the polyvinyl chloride polymer having reactive groups at both ends, the temperature, time, and amount of ozone during the reaction between the polyvinyl chloride polymer and ozone.
The chain length of the hydrophilic polymer having a reactive group at one end can be selected by selecting the molecular weight of the hydrophilic polymer having a reactive group at one end by reprecipitation method or fractional precipitation method. It is possible.

First, the medical material according to the present invention can provide a material designed at a molecular level, so that a medical material suitable for desired material properties can be easily produced.

In the medical device according to the present invention, a biocompatible device surface can be easily created.

The vinyl chloride-based M14 resin hydrophilic agent according to the present invention is the first
By using a block copolymer synthesized from a polyvinyl chloride polymer and a hydrophilic polymer, a hydrophilic agent having an arbitrary degree of hydrophilicity and good compatibility with vinyl chloride resins can be produced. This makes it possible to make the surface of vinyl resin hydrophilic. Second, hydrophilizing agents can be used in various ways, such as dissolving them in a solvent and coating them, dissolving them by heating and coating them, and molding them after adding them to vinyl chloride resin. It is also possible to make it hydrophilic later. Thirdly, the hydrophilic agent does not elute from the surface treated with the hydrophilic agent of the present invention, and the hydrophilicity of the surface can be maintained for a long time, and it can be used for food and medical purposes.

Furthermore, the molded article according to the present invention that deforms upon contact with water is firstly molded by combining an A-B-A type block copolymer synthesized from polyvinyl chloride and polyethylene glycol with a flexible material. This has made it possible to produce molded products that deform from their original shape when they come into contact with water.

Second, the plastic material to be used is not limited to resin, and can be selected from a wide selection range such as fibers, paper, inorganic materials, and metals.

Thirdly, molding for this purpose is possible by dissolving the block copolymer in a solvent or by heating it, and conventional molding techniques can be used as is, making it inexpensive and easy to manufacture. It is. Furthermore, the fourth
In addition, the deformation is caused by contact with water, is fast, and is reversible and can be used many times. Fifth, by covering the surface of the molded article with a water-containing or water-permeable material, the time required for deformation can be extended, and the deformation time can be adjusted and controlled.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the infrared absorption spectrum of the novel ABA type block copolymer F produced according to the present invention. FIG. 2 shows the novel A produced in Example 2 according to the present invention.
It is a figure which shows the infrared absorption spectrum of BA type block copolymer A1. FIGS. 3A and 3B are cross-sectional views of a molded article according to the present invention that deforms when it comes into contact with water, and the molded article after the deformation. FIG. 4 is a sectional view of a molded product of the present invention whose surface is partially covered with poly-2-hydroxyethyl methacrylate. FIGS. 5A and 5B are perspective views showing the catheter molded article of the present invention to prevent falling off, and its structure after deformation. FIG. 6 is an explanatory diagram of a rod-shaped molded product for a guide wire according to the present invention. FIG. 7 is an explanatory diagram of a tubular molded product for a catheter according to the present invention. [Explanation of symbols of main parts] 1. Block copolymer of the present invention 2. Vinyl chloride 3. Water-containing St. 1 Figure 1

Claims (9)

[Claims] (1) General formula A-B-A (A is a hydrophilic polymer, B
is a vinyl chloride polymer). (2) The block copolymer according to claim 1, wherein the hydrophilic polymer is an ethylene glycol polymer or a 2-hydroxyethyl methacrylate polymer. (3) A claim characterized in that a hydrophilic polymer having a reactive group at one end and a vinyl chloride polymer having a reactive group reacting with the reactive group at both ends are added and reacted. A method for producing a block copolymer according to 1 or 2. (4) A biocompatible medical material containing the block copolymer according to claim 1 or 2. (5) A medical device, characterized in that the block copolymer according to claim 1 or 2 is formed on at least the surface of a medical device. (6) A surface hydrophilic agent for vinyl chloride resin containing the block copolymer according to claim 1 or 2. (7) A hydrophilic vinyl chloride resin containing the block copolymer according to claim 1 or 2. (8) A surface-hydrophilic vinyl chloride resin molded article, characterized in that the block copolymer according to claim 1 or 2 is formed on at least the surface thereof. (9) It is characterized by being composed of a combination of a block copolymer represented by the general formula A-B-A (A is an ethylene glycol polymer, and B is a vinyl chloride polymer) and a plastic material. Water-contact deformable molded product. ((10) Consisting of a combination of a block copolymer represented by the general formula A-B-A (A is an ethylene glycol polymer, B is a vinyl chloride polymer) and a plastic material, at least part of the surface A water-contact deformable molded article, characterized in that part of the article is covered with a water-containing or water-permeable material.