JPH0919493A - Material composition, its preparation, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding applicable to a part requiring a high expansion ratio which has low toxicity, high tearing strength, tensile strength and elongation, and small permanent elongation, and a material composition for providing this molding. SOLUTION: After 100mmol of diphenylmethane diisocyanate and 50mmol of polyoxytetramethylene glycol having a number average molecular weight of 1000 and a weight average molecular weight/number average molecular weight of 1.85 are mixed together to perform a polyaddition reaction, 30mmol of polyoxytetramethylene glycol having a number average molecular weight of 1000 and a weight average molecular weight/number average molecular weight of 1.85, 17mmol of 1,4-butanediol, and 2mmol of trimethylolpropane are added thereto to perform a polyaddition reaction, thereby providing the material composition. This composition is molded into a sheet, allowed to stand in a constant temperature equipment of 110 deg.C for 24 hours, thereby providing a molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article and a material composition, and more particularly to a portion of a catheter such as a balloon requiring a high expansion / contraction ratio, or a catheter requiring high kink resistance or bending resistance. Applicable to tubes,
The present invention relates to a molded product having low toxicity, high tear strength, tensile strength and elongation and small permanent elongation, and a material composition for obtaining the molded product.

[0002]

2. Description of the Related Art A multi-lumen catheter tube is used to impart many functions to a catheter used for treatment of a living body. Since the thickness of the tube wall is extremely thin, the tube is required to have high tensile strength, tensile elongation and tear strength and not to kink when bent. In addition, the dilatation body (balloon) of the dilatation catheter and the pump portion of the auxiliary artificial heart are required to have high tensile strength, tensile elongation, and tear strength because they repeat expansion and contraction. When the balloon or the like is deflated, wrinkles are formed, and it is required that the permanent elongation is small in order to prevent the occurrence of thrombus due to the retention of blood. Further, it is required that the coating material on the inner surface of the pump portion of the auxiliary artificial heart does not come off during long-term use. The catheter tube is required to have high strength, softness, elasticity, kink resistance and bending tendency. A tube that is easy to kink is liable to obstruct the lumen, which makes it difficult to expand the balloon and inject a drug solution. A tube that has a tendency to bend has poor operability. Multi-lumen tubes are generally easier to kink due to the thinner walls. But,
If a soft material is used to prevent kinking, it is likely to be deformed (bending habit) and the operability is impaired. A material with a large permanent elongation is easily deformed, and a material with a small permanent elongation is easily kink. Therefore, the medical molded article must have a good balance of these contradictory properties. BACKGROUND ART Thermoplastic polyurethanes such as polyether polyurethanes are well known as materials for obtaining molded products such as catheters, dilators, and artificial hearts. The polyether-based thermoplastic polyurethane is a polymer obtained by polyaddition reaction of diisocyanate and diol or diamine at substantially equal molar ratios. However, when a tube for a multi-lumen catheter is molded using this thermoplastic polyurethane, the strength and the like are insufficient and a kink is likely to occur. Also, like a balloon of a balloon catheter, 500
When applied to a portion requiring a high expansion and contraction rate of not less than%, wrinkles easily occur on the balloon surface when the balloon is deflated, and the prevention of thrombus generation is insufficient.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a molded article having low toxicity, high tear strength, tensile strength and elongation and small permanent elongation, particularly a catheter tube, an expandable body (balloon) and an auxiliary artificial heart. The present invention provides a medical molded article and a material composition for obtaining the molded article. As a result of earnest studies to achieve this object, the present inventors have found that the above object can be achieved by using a polyurethane obtained by using a polyether having a narrow molecular weight distribution, and based on this finding, The present invention has been completed.

[0004]

Thus, according to the present invention, (1) a number average molecular weight of 600 to 3,000 and a weight average molecular weight / number average molecular weight value of less than 2.0, and the weight ratio of the isocyanate group to the Containing a polyether compound (a) having two or more functional groups that undergo an addition reaction, a compound (b) having a molecular weight of 500 or less and having two or more functional groups that undergo a polyaddition reaction with an isocyanate group, and a polyfunctional isocyanate (c) Wherein the amount of the functional group which undergoes a polyaddition reaction with the isocyanate group in the polyether compound (a) is 10 to 105 moles based on 100 moles of the isocyanate group in the polyfunctional isocyanate (c). And the amount of the functional group that undergoes a polyaddition reaction with the isocyanate group in the compound (b) is 0 to 50 mol based on 100 mol of the isocyanate group in the polyfunctional isocyanate (c). And the total amount of the functional groups that undergo a polyaddition reaction with the isocyanate group in the polyether compound (a) and the compound (b) is the polyfunctional isocyanate (c).
60 to 105 relative to 100 moles of the isocyanate group in
There is provided a material composition characterized in that it is molar.

The following are provided as preferred embodiments of the material composition of the present invention. (2) The above-mentioned (1), wherein the polyfunctional isocyanate (c) is diphenylmethane diisocyanate.
Material composition. (3) The material composition according to (1) above, wherein the polyether compound (a) is polyoxytetramethylene glycol.

(4) The material composition according to (1) above, wherein the compound (b) is trimethylolpropane, ethylenediamine or 1,4-butanediol. (5) Compound (b) is used in combination with a compound (b1) having two functional groups capable of polyaddition reaction with an isocyanate group and a compound (b2) having three or more functional groups capable of polyaddition reaction with an isocyanate group. The material composition according to (1) above.

(6) The amount of the functional group which undergoes the polyaddition reaction with the isocyanate group in the bifunctional compound (b1) is the amount of the compound (b1).
50 to 95 mol% based on the total amount of the functional groups capable of polyaddition reaction with the isocyanate group in the compound (b2), and the functional group capable of polyaddition reaction with the isocyanate group in the trifunctional or higher functional compound (b2). In the compound (b1) and the compound (b
5 to 50 mol% based on the total amount of the functional groups which undergo a polyaddition reaction with the isocyanate group in 2) [however, the compound (b1)
And the compound (b2) in an amount of 100 mol%] in total, the bifunctional compound (b1) and the trifunctional or higher functional compound (b).
2. The material composition according to the above (5), characterized in that 2) is used. (7) The bifunctional compound (b1) is ethylenediamine or 1,4-butanediol, and the trifunctional or higher functional compound (b)
2) is a trimethylol propane, The material composition of said (5) or (6) characterized by the above-mentioned.

According to the present invention, (8) after mixing a part of the polyether compound (a) and the polyfunctional isocyanate (c), the rest of the polyether compound (a) and the compound (b) are added thereto. A method for preparing the material composition according to (1) above is provided.

The following are provided as preferred embodiments of the method for preparing the material composition of the present invention. (9) The amount of the functional group which undergoes a polyaddition reaction with the isocyanate group in the compound (a) is 35 to 65 mol per 100 mol of the isocyanate group in the polyfunctional isocyanate (c). After mixing the isocyanate (c) and the compound (a) and heating, the compound (a) is added to 100 mol of the isocyanate group in the polyfunctional isocyanate (c).
The amount of functional groups that undergo a polyaddition reaction with the isocyanate groups in the
To 70 mol (provided that the total amount of the functional groups capable of polyaddition reaction with the isocyanate group in the compound (a) is 40 to 105 mol) and the functional group capable of polyaddition reaction with the isocyanate group in the compound (b). The method for preparing (8), wherein the compound (a) and the compound (b) are added in an amount of 0 to 50 mol. (10) The preparation method according to (9) above, wherein the heating temperature is 50 to 100 ° C. in the absence of a catalyst.

Further, according to the present invention, (11) the polyether compound (a), the compound (b) and the polyfunctional isocyanate (c) constituting the material composition according to any one of the above (1) to (7). ) And a polyaddition reaction are provided.

The following are provided as preferred embodiments of the molded article of the present invention. (12) The molded product according to (11), which is obtained by heating the material composition according to any one of (1) to (7) to 80 to 170 ° C. to carry out a polyaddition reaction. (13) Catheter tube obtained by polyaddition reaction of the polyether compound (a), the compound (b) and the polyfunctional isocyanate (c) constituting the material composition according to any one of (1) to (7) above. . (14) For a catheter obtained by polyaddition reaction of a polyether compound (a), a compound (b) and a polyfunctional isocyanate (c) constituting the material composition according to any one of (1) to (7) above. balloon. (15) Auxiliary artificial body obtained by polyaddition reaction of the polyether compound (a), the compound (b) and the polyfunctional isocyanate (c) constituting the material composition according to any one of (1) to (7) above. Heart coating.

The material composition of the present invention contains a polyfunctional isocyanate (c) and a polyether compound (a) or compound (b) having a functional group that undergoes a polyaddition reaction with an isocyanate group having a specific molecular weight. It is a thing.

The polyether compound (a) used in the material composition of the present invention has two or more functional groups which undergo a polyaddition reaction with an isocyanate group. The functional group that undergoes a polyaddition reaction with the isocyanate group is a functional group having active hydrogen. Specific examples thereof include a hydroxyl group and an amino group.
In addition, active hydrogen refers to a hydrogen atom bonded to an oxygen atom or a nitrogen atom which forms part of a compound.

The polyether compound (a) having a functional group capable of undergoing a polyaddition reaction with an isocyanate group has a lower limit of the number average molecular weight of 600, preferably 800, and an upper limit of 3000, preferably 1500. When it is less than 600, the tensile strength and elongation of the molded product obtained by subjecting the material composition to the polyaddition reaction are small. On the other hand, if it exceeds 3000, the permanent elongation of the molded product becomes large. The number average molecular weight of the polyether compound (a) is a value obtained by measuring it with tetrahydrofuran as a carrier using gel permeation chromatography and obtaining it based on a calibration curve of the number average molecular weight of standard polystyrene.

The polyether compound (a) having a functional group capable of undergoing a polyaddition reaction with an isocyanate group has a weight average molecular weight / number average molecular weight value of less than 2, preferably 1.9 or less. If it exceeds 2, the permanent elongation of the molded article increases and the strength decreases. The weight average molecular weight of the polyether compound (a) is a value determined by using gel permeation chromatography with tetrahydrofuran as a carrier and based on a calibration curve of the weight average molecular weight of standard polystyrene.

Specific examples of the polyether compound (a) having a functional group which undergoes a polyaddition reaction with an isocyanate group include:
Examples thereof include polyether polyols such as polyoxytetramethylene glycol, polyethylene glycol and polypropylene glycol. The polyether compound (a) can be used alone or in combination of two or more. Of these polyether compounds (a), polyoxytetramethylene glycol is preferable because it is biocompatible and safe.

The amount of the polyether compound (a) is such that the amount of the functional group which undergoes a polyaddition reaction with the isocyanate group in the polyether compound (a) is 100 mol of the isocyanate group in the polyfunctional isocyanate (c). 10-105 moles,
It is preferably 40 to 100 mol.
If it is less than 10 mol, the permanent elongation of the molded article becomes large and the elongation becomes small. On the other hand, if it exceeds 105 moles, the permanent elongation increases and the tensile strength decreases.

The polyfunctional isocyanate (c) used in the material composition of the present invention is a compound having two or more isocyanate groups. Specifically, aromatic isocyanates such as diphenylmethane diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, tetramethyl xylene diisocyanate, and xylene diisocyanate; dicyclohexane diisocyanate, dicyclohexylmethane diisocyanate, Examples include aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate. Of these polyfunctional isocyanates, diphenylmethane diisocyanate is preferable because it is highly safe for living organisms.

In order to increase the strength of the molded article obtained by the material composition of the present invention, the material composition contains 2 or more functional groups which have a weight average molecular weight of 500 or less, preferably 300 or less and which undergo a polyaddition reaction with an isocyanate group. It is preferable that the compound (b) having one or more units is contained as a component. The strength of the molded article does not increase even if a material having a large mass average molecular weight is used. The molecular weight of the compound (b) is a value obtained by measurement using a mass spectrum.

Specific examples of the compound (b) include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, methyleneglycoside, and sorbitol. Polyols such as sugars; polyols such as ethylenediamine, hexamethylenediamine, N, N'-diisopropylmethylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, 1,3,5-triaminobenzene; oximes And so on. Compound (b)
Among them, trimethylolpropane, ethylenediamine or 1,4-butanediol is preferably used because the strength of the molded product is increased by using these.

The amount of the compound (b) is usually such that the amount of the functional group which undergoes the polyaddition reaction with the isocyanate group in the compound (b) is 100 mol with respect to 100 mol of the isocyanate group in the polyfunctional isocyanate (c). It is substituted with the polyether compound (a) in an amount of 0 to 50 mol, preferably 1 to 40 mol.
If it exceeds 50 moles, the elongation of the molded product becomes small.

The compound (b) can be used in combination of two or more kinds. Those having two functional groups that undergo a polyaddition reaction with an isocyanate group (hereinafter referred to as a bifunctional compound (b
It may be 1). ) And a compound having three or more functional groups that undergo a polyaddition reaction with an isocyanate group (hereinafter sometimes referred to as a trifunctional or higher functional compound (b2)), the tear strength and the tensile strength increase, It is also preferable because the permanent elongation becomes small. In particular, it is preferable to use ethylenediamine or 1,4-butanediol as the bifunctional compound (b1), trimethylolpropane as the trifunctional or higher functional compound (b2), and to combine them.

When the bifunctional compound (b1) and the trifunctional or higher functional compound (b2) are used in combination, the amount of the bifunctional compound (b1) is the polyaddition reaction with the isocyanate group in the bifunctional compound (b1). The amount of the functional group to be added is usually 50 to 95 mol%, preferably 70 to 90 mol% with respect to the total amount of the functional groups that undergo a polyaddition reaction with the isocyanate group in the compound (b1) and the compound (b2). It becomes the ratio of. If it is less than 50 mol%, the elongation and tear strength of the molded product will be small. On the other hand, when it exceeds 95 mol%, the effect of increasing the tear strength and the tensile strength of the molded article is lost. The amount of the trifunctional or higher functional compound (b2) is such that the amount of the functional group that undergoes a polyaddition reaction with the isocyanate group in the trifunctional or higher functional compound (b2) is equal to that of the isocyanate group in the compound (b1) or in the compound (b2). Normally, 5 is added to the total amount of functional groups that undergo polyaddition reaction.
To 50 mol%, preferably 10 to 30 mol%.

Polyether compound (a) and compound (b)
And the total amount of the functional groups reacting with the isocyanate group in the polyether compound (a) and the compound (b) in a polyaddition reaction is 100 moles of the isocyanate group in the polyfunctional isocyanate (c). , 60 to 105 mol, preferably 8
It is in the range of 0 to 100 mol. If it deviates from this range, the permanent elongation will increase.

In the material composition of the present invention, if necessary,
Fillers such as colloidal silica, white carbon and calcium carbonate; plasticizers such as dibutyl phthalate, di (2-ethylhexyl) phthalate and di (2-ethylhexyl) adipate; and softeners such as white oil and paraffin can be added.

The material composition of the present invention is usually in the form of a solution of an organic solvent or a solution which is heated and mixed without a solvent. The organic solvent used for the solution is usually one that is incompatible with water or an aqueous solution obtained by being compatible with water has a pH of 6
~ 8. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofutan and cyclohexanone; ketones such as methyl ethyl ketone and isobutyl ethyl ketone; and aliphatic hydrocarbons such as hexene and hexane.

The material composition of the present invention is not limited by its method of preparation. The preparation is usually carried out by mixing the polyfunctional isocyanate (c) and the polyether compound (a),
A solution of the compound (b) is added, or the polyether compound (a) and the compound (b) are mixed and then the polyfunctional isocyanate (c) is added, or the polyfunctional isocyanate (c) and the polyether are added. After mixing with a part of the compound (a), the balance of the polyether compound (a) and the compound (b)
Is added. Of these preparation methods,
Preparation in which a polyfunctional isocyanate (c) and a part of the polyether compound (a) are mixed and reacted to obtain a urethane prepolymer, and then the rest of the polyether compound (a) and the compound (b) are added thereto The method is suitable for increasing the tensile strength and the like.

After mixing the polyfunctional isocyanate (c) and a part of the polyether compound (a) (first stage), the rest of the polyether compound (a) and the compound (b) were added thereto.
In the second step), the amount of the polyether compound (a) mixed with the polyfunctional isocyanate (c) in the first step is determined by the amount of the isocyanate in the polyether compound (a). The amount of the functional group that undergoes a polyaddition reaction with the group is usually 35 to 65 mol, preferably 40 to 6 with respect to 100 mol of the isocyanate group in the polyfunctional isocyanate (c).
The range is 0 mol. Less than 35 mol or 65
If it exceeds the molar amount, the effect of increasing the tensile strength and the like becomes small. It is preferable to heat at the time of mixing the polyfunctional isocyanate (c) and a part of the polyether compound (a) or after the mixing. By heating, the polyfunctional isocyanate (c) and a part of the polyether compound (a) undergo a polyaddition reaction. The heating temperature is usually 50 to 100 ° C, preferably 60 to 90 ° C. If it is less than 50 ° C, it takes time to bond, and conversely, if it exceeds 100 ° C, the second step operation becomes difficult, and the permanent elongation of the molded product increases,
Also, the tensile strength, tear strength and elongation are reduced. The heating time is usually 10 to 480 minutes, preferably 30 to 120 minutes.

A molded product can be obtained by subjecting the polyfunctional isocyanate (c) constituting the material composition of the present invention to the polyaddition reaction with the polyether compound (a) and the compound (b). The molded article of the present invention can be obtained by subjecting the material composition to polycondensation reaction either before or after molding, preferably partially polyaddition reaction before molding, and further polyaddition reaction after molding. Molding is usually performed by a melt molding method, a casting molding method, a dipping molding method, a reactive extrusion molding method, or the like. For example, in the dipping molding method,
A mold having a desired shape is dipped in a solution of the material composition in an organic solvent, pulled up, and left to stand. In the reactive extrusion molding method, a urethane prepolymer obtained by polyaddition reaction of a part of the polyether compound (a) and the polyfunctional isocyanate (c), the remainder of the polyether compound (a) and the compound (b)
While mixing and heating the mixed liquid of 1), extrusion molding is performed using an extruder.

The polyaddition reaction is carried out by heating the material composition. Heating is a solvent contained in the material composition,
The amount of volatile components such as the dispersion medium, relative to the material composition,
Usually, it is preferable to perform the treatment after removing 3 wt% or less, preferably 0.5 wt% or less. If it exceeds 3% by weight, the composition upon heating foams and voids are formed in the molded product, which is not preferable.

The heating temperature is usually 50 to 170 ° C, preferably 100 to 130 ° C. If it is less than 50 ° C, the polyaddition reaction is difficult, and if it exceeds 170 ° C, a decomposition reaction occurs and the molded product tends to deteriorate. The heating time varies depending on the shape of the molded product, but is usually 12 to 120 hours,
It is preferably 24 to 72 hours. When the time is short, the permanent elongation of the molded product becomes large, and when the time is long, the tensile strength of the molded product decreases. A catalyst may be added to carry out the polyaddition reaction at a heating temperature of 50 ° C. or lower. Examples of the catalyst include tertiary amines and organometallic catalysts. After the polyaddition reaction, it is usually preferable to allow the polyaddition reaction product (molded product) to mature for 4 to 14 days at room temperature.

[0032]

The molded article of the present invention has a larger tensile strength, tear strength, etc. and a smaller permanent elongation than those molded using the conventional thermoplastic polyurethane. Therefore, when it is applied to an expandable body (balloon). It reduces the occurrence of blood clots, makes it less likely to cause kinks and bending habits when applied to catheter tubes (including catheter introducers, etc.), and contracts and expands hundreds of thousands of times when applied to coating materials such as artificial hearts. The coat is hard to peel off. The material composition of the present invention can be applied to other artificial blood vessels, artificial valves and the like.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

The evaluation method performed in this example will be described below. (Tensile test) A 2 mm thick sheet was used as a No. 3 dumbbell (JI
Stamped with SK6301), and this is JIS K-63
01, chuck distance 20 mm, pulling speed 50
The elongation at tensile rupture and the tensile strength were determined under the conditions of 0 mm / min, temperature 23 ° C., and relative humidity 65%.

(Permanent elongation) A sheet having a thickness of 2 mm was punched out with a No. 3 type dumbbell (JIS K6301), and marked lines were marked on the surface of the sheet at intervals of 2 cm in the tensile direction. Distance between chucks 20 mm, pulling speed 500 mm / min, temperature 23
It was pulled at a temperature of 65 ° C. and a relative humidity of 65% until it reached an elongation of 500%, and held in that state for 10 minutes. After removing the force, the sample was allowed to stand for 10 minutes and the interval between the marked lines was measured. The difference between the marked line intervals before and after the pulling was determined by the ratio (%) to the marked line interval before the pulling (2 cm), which was taken as the permanent elongation.

(Antithrombogenicity) Vitro Test A material composition was applied to the inner surface of a 10 cm ³ test tube, and then left in a thermostat at 110 ° C. for 24 hours to give a coating (molded product).
I got 1 cm ³ of blood was poured into this test tube, and the mixture was shaken lightly at 37 ° C., the time until the fluidity of the blood disappeared was measured, and evaluated by the following indexes. ◎ ・ ・ ・ 30 minutes or more ○ ・ ・ ・ 25 minutes or more and less than 30 minutes △ ・ ・ ・ 20 minutes or more and less than 25 minutes × ・ ・ ・ less than 20 minutes Vivo test A balloon catheter was inserted from the vena cava of a goat to the vicinity of the right atrium. After that, physiological saline was pressed into the catheter to inflate the balloon to a diameter of 1 cm and left for 10 minutes,
Then, the balloon catheter was deflated, and after 3 days from the deflation, the balloon catheter was taken out from the vena cava, and the surface of the balloon portion was visually observed for the presence or absence of thrombus. ⊚: No thrombus has occurred (less than 3% of the surface of the balloon portion). ◯: Slight thrombus has occurred (3% or more and less than 20% of the surface of the balloon portion). Δ: Thrombus is partially generated (20% or more and less than 80% of the surface of the balloon portion). X: Thrombus is generated on the entire surface (80% or more of the surface of the balloon portion).

(Comprehensive evaluation as a balloon material for catheters) Tensile strength of 15 MPa or more, elongation of 600% or more,
When the permanent elongation was 20% or less and the evaluations in the vivo test were from ∘ to ⊚, the mark was ◯, and when not, the mark was x.

(Kink resistance test) At room temperature of 20 ° C., a tube for a catheter having a diameter of 2.3 mm was placed on two bases with a space of 40 mm, and the tubes at the same distance from the base were placed. Press at a speed of 5 mm / min from the top,
The displacement length of the tube when a kink occurred was determined.

(Deformation Test) A catheter tube having a length of 200 mm in the axial direction and a diameter of 2.3 mm was connected to both ends with adhesive tape, bent into a ring, and left in a thermostat at 50 ° C. for 30 minutes. Then remove the tape from both ends of the tube and
After leaving it in a 0 ° C. room for 10 minutes, the axial length of the tube was measured to determine the rate of change in length.

(Comprehensive evaluation as a catheter tube) Tensile strength, elongation, kink resistance, deformation resistance, etc. were comprehensively judged and evaluated as ◯.

(Evaluation of Adhesive Strength) Sheets of the antithrombotic material attached to the pumps of the two auxiliary artificial hearts obtained under the same conditions were immediately used for one, the other for 200,000 times at 37 ° C.
After 5% elongation, the strength [kN / m] at the time of peeling at 37 ° C. and a peeling speed of 100 mm / min was measured, and 2
The ratio of the peeling strength after the 200,000 times stretching to the peeling strength before the 10,000 times stretching was determined.

Example 1 A reactor purged with nitrogen was charged with 100 mmol of diphenylmethane diisocyanate and 50 mmol of polyoxytetramethylene glycol having a number average molecular weight of 1000 and a weight average molecular weight / number average molecular weight = 1.85 at 90 ° C. 1
Urethane prepolymer was obtained by polyaddition reaction for time. Further, 30 mmol of polyoxytetramethylene glycol having a number average molecular weight of 1000 and a weight average molecular weight / number average molecular weight of 1.85, 17 mmol of 1,4-butanediol and 2 mmol of trimethylolpropane (prolonging agent) were added to the reactor. The mixture was added and mixed with stirring at 70 ° C. to obtain a material composition. This material composition was defoamed for 3 minutes using a vacuum pump, poured into a gap (2 mm interval) between two 10 cm square iron plates, left in a thermostat at 110 ° C. for 24 hours, and then a sheet having a thickness of 2 mm ( A molded product) was obtained. The evaluation results of this sheet are shown in Table 1.

In a reactor purged with nitrogen, 100 mmol of diphenylmethane diisocyanate and a number average molecular weight of 10 were added.
00, and 50 mmol of polyoxytetramethylene glycol having a weight average molecular weight / number average molecular weight = 1.85 were added to carry out a polyaddition reaction at 90 ° C. for 1 hour. Furthermore, the number average molecular weight is 1000, and the weight average molecular weight / number average molecular weight is 1.8.
5 mmol of polyoxytetramethylene glycol (5), 17 mmol of 1,4-butanediol and 2 mmol of trimethylolpropane were dissolved in dry dioxane, diluted 20 times, added to the reactor, and added at 100 ° C.
After stirring and reacting for a time, the viscosity is increased to 3000 to 5000c.
After adjusting to p, a solution of the material composition was obtained. A Teflon-coated stainless steel rod having a diameter of 1.8 mm and a length of 100 mm was immersed in this solution, the solution was attached to the rod, the rod was lifted from the solution and left at room temperature to evaporate and remove tetrahydrofuran. Further, the polyaddition reaction was performed by leaving it in a thermostat at 110 ° C. for 24 hours to obtain a 0.15 mm-thick tube (molded product) with one end blocked. This tube was cut into a length of 13 mm and attached so as to cover the balloon side hole at the tip of a commercially available catheter having a diameter of 1.8 mm to obtain a balloon catheter. The evaluation results of the antithrombotic property of this balloon catheter are shown in Table 1.

Examples 2-8 and Comparative Examples 1-7 A material composition was prepared in the same manner as in Example 1 except that the kinds or amounts of the compounds used in Example 1 were changed to those shown in Table 1 or Table 2. A sheet and balloon catheter were obtained. The evaluation results of the sheet and balloon catheter are shown in Table 1 or Table 2.

[0045]

[Table 1]

[0046]

[Table 2]

From Tables 1 and 2, the molded product obtained by the polyaddition reaction of the material composition using the polyether compound (a) having a wide molecular weight distribution has a poor balance of tensile strength, elongation and permanent elongation, or a balloon. It can be seen that thrombus is likely to occur when applied to a part. On the other hand, the molded product obtained by the polyaddition reaction of the material composition using the polyether compound (a) having a narrow molecular weight distribution of the present invention has a large tensile strength and elongation and a small permanent elongation, and even when applied to the balloon portion. It can be seen that blood clots are unlikely to occur. In particular, when a compound (b1) having two functional groups that undergo a polyaddition reaction with an isocyanate group and a compound (b2) having three or more functional groups that undergo a polyaddition reaction with an isocyanate group are used in combination, It can be seen that the tensile strength is higher and the permanent elongation is smaller.

Example 9 A material composition and a sheet were obtained in the same manner as in Example 1 except that the kinds or amounts of the compounds used in Example 1 were changed to those shown in Table 3. On the other hand, the material composition was agitated by a gear pump type mixer (heated at 70 ° C.) to give 120
15atm, 2m in a cylindrical column heated to ~ 150 ° C
It was extruded at a speed of 1 / sec to obtain a 5-lumen tube having a diameter of 2.3 mm. This tube is 110 ℃ 110 ℃
It was left in the incubator for 24 hours for polyaddition reaction to obtain a catheter tube.

Example 10 and Comparative Examples 8-9 A material composition was prepared in the same manner as in Example 9 except that the kinds or amounts of the compounds used in Example 9 were changed to those shown in Table 3.
A sheet and a catheter tube were obtained. Table 3 shows the evaluation results of the sheet and the catheter tube.

[0050]

[Table 3]

From Table 3, it can be seen that the molded product obtained by the polyaddition reaction of the material composition using the polyether compound (a) having a wide molecular weight distribution has poor kink resistance and deformation resistance. On the other hand, it is understood that the molded product obtained by the polyaddition reaction of the material composition using the polyether compound (a) having a narrow molecular weight distribution of the present invention has good kink resistance and deformation resistance.

Example 11 100 mmol of diphenylmethane diisocyanate was added to a nitrogen-substituted reactor and ethylene oxide having a number average molecular weight of 1,000 and a weight average molecular weight / number average molecular weight of 1.95 was used.
45 mmol of a propylene oxide copolymer (polymerization molar ratio: ethylene oxide / propylene oxide = 6/4) was added, and polyaddition reaction was carried out at 90 ° C. for 1 hour. Next, the number average molecular weight is 1000, and the weight average molecular weight / number average molecular weight = 1.
95 ethylene oxide-propylene oxide copolymer (polymerization molar ratio: ethylene oxide / propylene oxide = 6/4) 25 mmol, 1,4-butanediol 17
Mmol and dioxane were added, the mixture was stirred at 80 ° C. for 3 hours to cause a reaction, and then ethanol was added to stop the reaction to obtain a solution of the material composition. This solution was applied to the inner surface of the pump portion of a soft polyvinyl chloride-assisted artificial heart, and then a sheet made of a polyurethane-silicone antithrombotic material was stuck thereon to obtain a assisted artificial heart.

Comparative Example 10 A material composition and an auxiliary artificial heart were obtained in the same manner as in Example 11 except that the kinds or amounts of the compounds used in Example 11 were changed to those shown in Table 4. Table 4 shows the evaluation results.

[0054]

[Table 4]

From Table 4, it can be seen that the molded product obtained by the polyaddition reaction of the material composition using the polyether compound (a) having a wide molecular weight distribution has a large decrease in adhesive strength. On the other hand, it can be seen that the molded product obtained by subjecting the material composition using the polyether compound (a) having a narrow molecular weight distribution of the present invention to the polyaddition reaction has a small decrease in adhesive strength.

Claims (4)

[Claims] 1. A polyether compound having a number average molecular weight of 600 to 3000 and a weight average molecular weight / number average molecular weight value of less than 2.0 and having two or more functional groups capable of polyaddition reaction with an isocyanate group ( a) a composition containing a compound (b) having a molecular weight of 500 or less and having two or more functional groups that undergo a polyaddition reaction with an isocyanate group and a polyfunctional isocyanate (c), wherein the polyether compound (a) The amount of the functional group which undergoes a polyaddition reaction with the isocyanate group of is 10 to 105 moles based on 100 moles of the isocyanate group in the polyfunctional isocyanate (c), and the polyaddition with the isocyanate group in the compound (b) is performed. The amount of the functional group to react is 0 to 50 mol with respect to 100 mol of the isocyanate group in the polyfunctional isocyanate (c), and the polyether compound (a) and the compound The material composition, wherein the total amount of the functional groups that undergo a polyaddition reaction with the isocyanate group in (b) is 60 to 105 moles based on 100 moles of the isocyanate group in the polyfunctional isocyanate (c). . 2. A polyether compound having a number average molecular weight of 600 to 3000 and a weight average molecular weight / number average molecular weight value of less than 2.0 and having two or more functional groups capable of undergoing a polyaddition reaction with an isocyanate group ( After mixing a part of (a) with the polyfunctional isocyanate (c), the remainder of the polyether compound (a) and a compound having two or more functional groups that have a molecular weight of 500 or less and undergo a polyaddition reaction with an isocyanate group ( The method for preparing a material composition according to claim 1, wherein b) is added. 3. A molded product obtained by polyaddition reaction of the polyether compound (a), the compound (b) and the polyfunctional isocyanate (c), which constitutes the material composition according to claim 1. 4. A polyether compound having a number average molecular weight of 600 to 3000 and a weight average molecular weight / number average molecular weight value of less than 2.0 and having two or more functional groups capable of undergoing a polyaddition reaction with an isocyanate group ( a), a compound (b) having a molecular weight of 500 or less and having two or more functional groups capable of undergoing a polyaddition reaction with an isocyanate group, and a polyfunctional isocyanate (c).
A balloon obtained by polyaddition reaction of and, having a tensile strength of 15 MPa or more, an elongation of 600% or more and a permanent elongation of 20% or less.