JP2000038427A - Heat-resistant medicinal and medical material and container and sealable article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a medicinal and medical material capable of holding a sufficient mechanical strength and withstanding even high-temperature sterilization without causing the deformation even under high-temperature conditions as compared with that of a conventional thermoplastic elastomer. SOLUTION: This medicinal and medical material contains an aromatic vinylic monomer containing at least one selected from the group consisting of α-methylstyrene, p-methylstyrene, a vinylnaphthalene derivative and an indene derivative in the medicinal and medical material comprising an isobutylene-based block copolymer formed from a polymer block comprising (a) a monomer component consisting essentially of isobutylene and a polymer block consisting essentially of (b) the aromatic vinylic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical / medical material excellent in heat resistance, gas permeation resistance and water vapor permeation resistance, and a container and a sealable article made of the same.

[0002]

2. Description of the Related Art Conventionally, as medical / medical materials represented by medical / medical containers and sealable articles, plasticized polyvinyl chloride resins, natural rubber, butyl rubber, isoprene rubber, styrene-butadiene are known. Rubber materials such as rubber are used.

[0003] The plasticized polyvinyl chloride resin is excellent in flexibility and flexibility, but has problems such as bleeding out of a plasticizer and residual ethylene oxide during sterilization with ethylene oxide. When it is used, it generally has a problem that a large-scale apparatus is necessary because a persulfurization step is required, and that recycling is difficult. To improve these, for example, Japanese Patent Application Laid-Open No. 5-212104 proposes a medical / medical sealable article comprising a block copolymer of an aromatic vinyl compound and isobutylene.
No. 9201 proposes a medical / medical container comprising the same block copolymer as described above.

[0004] Since these block copolymers can be molded in an unvulcanized state, they are excellent in moldability and recyclability as compared with conventional rubber materials, and do not use a vulcanizing agent or the like. Therefore, the problem of drug elution has also been improved. However, the aromatic vinyl monomer proposed in the above publication is styrene, and has a glass transition temperature as low as about 100 ° C., so that under high temperature conditions of 70 to 80 ° C. or more,
There were problems such as the strength, elasticity, etc. of the block body being reduced and the sealable article being melted and deformed. Furthermore, when these are used for rubber stoppers and the like, when the articles are exposed to high-temperature conditions, they are deformed, so that there is a problem that sufficient sealing properties and gas permeability resistance as a container cannot be secured. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to prevent deformation under high-temperature conditions, maintain sufficient mechanical strength, and maintain high-temperature sterilization as compared with conventional thermoplastic elastomers. An object of the present invention is to provide a medical / medical material that can withstand the above.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the heat resistance of the block body has been greatly reduced by using a specific aromatic vinyl monomer. The present invention has been found to provide a medical / medical material having excellent heat resistance and excellent heat resistance.

That is, the present invention provides an isobutylene formed from a polymer block composed mainly of a monomer component (a) containing isobutylene as a main component and a polymer block composed mainly of an aromatic vinyl monomer (b). A medical / medical material comprising a block copolymer, wherein the aromatic vinyl monomer is at least one selected from the group consisting of α-methylstyrene, p-methylstyrene, vinylnaphthalene derivatives and indene derivatives Pharmaceuticals characterized by containing
It is a medical material.

[0008] The aromatic vinyl monomer (b) is α-
It is preferably methylstyrene and / or indene, and may also consist of a mixture of styrene and α-methylstyrene and / or indene.

In the above case, 0 to 95 mol% of styrene and α
-Methyl styrene and / or indene 100 to 5 mol%
It is preferably a mixture with

The isobutylene-based block copolymer comprises a polymer block mainly composed of an aromatic vinyl monomer-a polymer block mainly composed of isobutylene-an aromatic vinyl monomer. Triblock copolymer formed from a polymer block, a polymer block containing an aromatic vinyl monomer as a main component-a diblock copolymer formed from a polymer block containing isobutylene as a main component, or These mixtures can be used, and the ratio of each block is such that a polymer block mainly composed of an aromatic vinyl monomer is 5 to 80 parts by weight and a polymer block mainly composed of isobutylene is 95 to 95 parts by weight. It is preferable that the block copolymer is composed of 20 parts by weight, and the polymer block containing an aromatic vinyl monomer as a main component has 15 to 40 parts by weight of isobutylene. Polymer block component 85
More preferably, it is a block copolymer consisting of ６０60 parts by weight.

The number average molecular weight of the isobutylene block copolymer is preferably from 30,000 to 500,000, more preferably from 50,000 to 400,000.

The above medical / medical materials can be used as medical containers or medical sealable articles, and are also suitable for medical tubes and rubber stoppers.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

According to the present invention, there is provided a medical / medical material comprising a polymer block comprising a monomer component (a) containing isobutylene as a main component and a polymer containing an aromatic vinyl monomer (b) as a main component. A pharmaceutical or medical material comprising an isobutylene-based block copolymer formed from blocks, wherein the aromatic vinyl-based monomer is a group consisting of α-methylstyrene, p-methylstyrene, a vinylnaphthalene derivative and an indene derivative. It is characterized by including at least one selected from the following.

Among the above-mentioned aromatic vinyl monomers, α-methylstyrene and indene are preferred in view of the balance between cost, physical properties and productivity.

In the block copolymer used in the present invention, an aromatic compound other than an aromatic vinyl monomer selected from the group consisting of α-methylstyrene, p-methylstyrene, vinylnaphthalene derivatives and indene derivatives is used. It may contain a vinyl monomer.

Styrene is preferred as another aromatic vinyl monomer from the viewpoint of the balance between cost and physical properties.

The proportion of the aromatic vinyl monomer containing a compound selected from the group consisting of α-methylstyrene, p-methylstyrene, a vinylnaphthalene derivative and an indene derivative is not particularly limited. 5%
Or more, more preferably 10% or more. If the above ratio is less than 5%, the heat resistance of the isobutylene-based block copolymer is not sufficiently improved.

Further, the combination of the aromatic vinyl monomers is preferably composed of a mixture of styrene and α-methylstyrene and / or indene. As for the mixing ratio, it is preferable that styrene is 0 to 95 mol% and α-methylstyrene and / or indene is 100 to 5 mol%.

The isobutylene-based block copolymer used in the present invention is a copolymer having a polymer block mainly composed of an aromatic vinyl monomer and a polymer block mainly composed of isobutylene. Any of these can be used, but from the viewpoint of balance of physical properties and simplicity of synthesis, a polymer block mainly composed of an aromatic vinyl monomer-a polymer block mainly composed of isobutylene-an aromatic vinyl series Triblock copolymer formed from polymer block mainly composed of monomer, polymer block mainly composed of aromatic vinyl monomer-formed from polymer block mainly composed of isobutylene Diblock copolymers or mixtures thereof are preferred.

The ratio of a polymer block (block A) containing an aromatic vinyl monomer as a main component of an isobutylene block copolymer and a polymer block (block B) containing isobutylene as a main component is particularly limited. However, from the balance of physical properties, a block copolymer composed of (block A) 5 to 80 parts by weight and (block B) 95 to 20 parts by weight is preferable, and (block A) 15 to 40 parts by weight, Block B) a block copolymer consisting of 85 to 60 parts by weight is more preferred.

The number average molecular weight of the block copolymer is not particularly limited, but the number average molecular weight of the block copolymer is preferably 30,000 to 500,000, more preferably 50,000.
0 to 400,000 is particularly preferred. Number average molecular weight is 3
If it is less than 000, mechanical properties and the like are not sufficiently exhibited, and if it exceeds 500,000, the moldability and the like are greatly reduced.

Regarding the method for producing the block copolymer,
Although not particularly limited, for example, in the presence of a compound represented by the following general formula (I), a monomer mainly composed of isobutylene and a monomer mainly composed of an aromatic vinyl unit are polymerized. Obtained by

[0024]

Embedded image (Wherein, a plurality of R ¹ are the same or different, .R ² representing a monovalent hydrocarbon group having a hydrogen atom or 1 to 6 carbon atoms, 1
Represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group. X represents a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, or an acyloxyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 6. When a plurality of Xs are present, they may be the same or different. As specific examples of the compound represented by the general formula (I),
(1-chloro-1-methylethyl) benzene, 1,4-
Bis (1-chloro-1-methylethyl) benzene, 1,
3-bis (1-chloro-1-methylethyl) benzene,
1,3,5-tris (1-chloro-1-methylethyl)
Benzene and 1,3-bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene are exemplified. Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene, or dicumyl chloride.

Among these, in terms of reactivity and availability,
Bis (1-chloro-1-methylethyl) benzene is particularly preferred.

In the present invention, first, a monomer component containing isobutylene as a main component is polymerized in the presence of the compound represented by the general formula (I) to have a substituent (X) at a terminal. After synthesizing an isobutylene polymer and isolating and purifying the polymer, an aromatic vinyl monomer is polymerized to synthesize a block copolymer.

Further, if necessary, a Lewis acid catalyst may coexist. Such a Lewis acid may be any as long as it can be used for cationic polymerization, and TiCl ₄ , T
iBr ₄ , BCl ₃ , BF ₃ , BF ₃ .OEt ₂ , SnCl ₄ , Sb
Cl ₅ , SbF ₅ , WCl ₆ , TaCl ₅ , VCl ₅ , FeCl ₃ ,
Metal halides such as ZnBr ₂ , AlCl ₃ and AlBr ₃ ; and organic metal halides such as Et ₂ AlCl and EtAlCl ₂ can be suitably used. Above all, considering the ability as a catalyst and the industrial availability, TiC
I ₄ , BCl ₃ , and SnCl ₄ are preferred.

The central metal of the Lewis acid catalyst may be the same as or different from the central metal of the metal compound, but the same metal atom is preferred in terms of post-polymerization treatment. In the present invention, the Lewis acid is usually used in an amount of 0.1 to 100 moles per mole of the compound represented by the above general formula (I), but the preferred amount is 0.3 to 50 times.
The range is twice as high.

Further, if necessary, an electron donor component can be present in the polymerization system. In the present invention, the electron donor component has a donor number of 15 to 60. Conventionally known ones can be widely used. Preferred electron donor components include, for example, pyridines, amines, amides, sulfoxides, and metal compounds having an oxygen atom bonded to a metal atom.

Further, if necessary, the polymerization reaction can be carried out in a solvent, and such a solvent is not particularly limited as long as it does not substantially inhibit cationic polymerization, and any solvent can be used. . Specifically, methyl chloride,
Halogenated hydrocarbons such as dichloromethane, n-propyl chloride, n-butyl chloride and chlorobenzene;
Alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene; ethane, propane, butane, pentane, hexane,
Linear aliphatic hydrocarbons such as heptane, octane, nonane, and decane; 2-methylpropane, 2-methylbutane,
Branched aliphatic hydrocarbons such as 2,3,3-trimethylpentane and 2,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; hydrogenated petroleum fractions Refined paraffin oil and the like can be mentioned.

These solvents are used alone or in combination of two or more in consideration of the balance between the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer.

The amount of each component can be appropriately designed depending on the characteristics of the desired polymer. First, the molecular weight of the obtained polymer can be determined from the molar equivalent relationship between the isobutylene-based monomer and a cationic polymerizable monomer different from isobutylene and the compound represented by the general formula (I).
Usually, the number average molecular weight of the obtained block copolymer is 20,
It is set to be about 000 to 500,000.

In the production method of the present invention, in conducting the actual polymerization, each component is mixed under cooling, for example, at a temperature of -100 ° C. or more and less than 0 ° C. In order to balance the energy cost with the stability of the polymerization, a particularly preferred temperature range is -80C to -30C.

When a block copolymer is produced, a Lewis acid, a compound represented by the general formula (I), an electron donor component,
The method and order of addition of the monomer components and the like are not particularly limited, but preferred methods include, for example,
(A) a step of polymerizing a monomer mainly composed of isobutylene in the presence of an initiator system comprising a compound represented by the general formula (I) and a Lewis acid, and an electron donor component; A method comprising a step of adding a monomer mainly composed of an aromatic vinyl unit to the system and polymerizing the same. On this occasion,
After the step (A), the polymer may be once isolated and purified, or the step (B) may be carried out without isolation.

The α-methylstyrene, p-methylstyrene, vinylnaphthalene derivative, and indene derivative used in the present invention may be added to the polymerization system either alone or as a mixture with other aromatic vinyl monomers. obtain.

In the isobutylene-based block copolymer used in the present invention, other cationically polymerizable monomers may be copolymerized as long as the performance of the pharmaceutical or medical material of the present invention is not impaired. Other cationically polymerizable monomers include aliphatic olefins, aromatic vinyls, dienes,
Vinyl ethers, silanes, vinyl carbazole, β
-Monomers such as pinene and acenaphthylene can be exemplified. These are used alone or in combination of two or more. The drug / medical material of the present invention may be composed of the above-mentioned isobutylene-based block copolymer alone or may be composed of a multilayer structure in combination with another thermoplastic resin. A thermoplastic resin or an additive can be added to the pharmaceutical or medical material of the present invention, if necessary, as long as the performance is not impaired. Examples of the thermoplastic resin include polyolefin-based resins, polyphenylene ether-based resins, aromatic vinyl compound-based resins, polycarbonate-based resins, polyamide-based resins, vinyl chloride-based resins, and styrene-based block copolymers (for example, butadiene-styrene block copolymers). Polymers, butadiene-isoprene block copolymers and hydrogenated products thereof).

Examples of the additives include stabilizers such as antioxidants and ultraviolet absorbers, lubricants, plasticizers, dyes, pigments, flame retardants, fillers, reinforcing materials, tackifiers, and other auxiliaries. Can be

Examples of the filler and reinforcing material include glass fiber, carbon black, flake graphite, carbon fiber, calcium sulfate, calcium carbonate, calcium silicate, alumina, silica, titanium oxide, talc, mica and the like.

As the tackifier, polybutene resin,
Known resins such as rosin resin (rosin, rosin ester or hydrogenated rosin), phenol resin, terpene phenol resin, xylene resin, aliphatic petroleum resin, terpene resin, and cumarone resin can be used. Among these, polybutene resins, rosin ester resins, terpene phenol resins, and the like are preferable. The tackifier is usually used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the block copolymer. Examples of the stabilizer include antioxidants such as hindered phenols, phosphate esters, and amines, and ultraviolet absorbers such as benzothiazole, benzotriazole, and benzophenone. Examples of the plasticizer include petroleum-based process oils such as paraffin-based process oils, naphthene-based process oils and aromatic process oils, natural oils such as castor oil, and liquid polymers such as liquid polybutene, liquid polybutadiene, and liquid polyisoprene. .

The pharmaceutical or medical material of the present invention can be prepared by a known method. For example, an isobutylene-based block copolymer and various compounding agents are mixed by a tumbler, a mixer, a blender or the like, and kneaded by a screw extruder, a roll, or the like, and a known method such as injection molding, extrusion molding, and compression molding. It can be formed into an arbitrary article by a method such as calender molding.

From the medicine / medical material of the present invention, heat resistance,
It is possible to obtain a container or a sealable article having excellent gas permeation resistance and water vapor permeation resistance.

Examples of the container include a drug container, a drug solution container, a blood container, a blood storage container, a sterilization bag container, an infusion bag container, and the like. As a preferred embodiment, it is preferable to use it as a medical tube.

On the other hand, examples of the sealable article include rubber stoppers for pharmaceutical products, gaskets for syringes, caps for syringes, rubber stoppers for blood collection tubes, and the like, with rubber stoppers being particularly preferred.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented within the scope of the invention. .

The properties of the polymer were measured according to the following methods. (1) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polymer Measured by gel permeation chromatography (GPC). Using a Waters 510 type GPC system, chloroform was used as the mobile phase, and the measurement was performed at a polymer concentration of 2 mg / ml and a column temperature of 35 ° C. The number average molecular weight and molecular weight distribution were calculated using polystyrene as a standard sample. (2) Glass transition temperature (Tg) of polymer Differential scanning calorimetry was performed using a DSC-7 manufactured by Perkin-Elmer under a nitrogen stream at a heating rate of 20 ° C./min. (3) Water vapor permeability coefficient of polymer A sample of about 1 mm thickness was prepared by press molding.
According to IS Z 0208, the permeability coefficient of oxygen at 40 ° C. and 90% RH was measured. (4) Oxygen Permeability Coefficient of Polymer A sample having a thickness of about 1 mm was prepared by press molding.
According to IS K 7126, the permeability coefficient of oxygen at 23 ° C. was measured.

[Production Example 1] (Synthesis of chlorine-terminated polyisobutylene) After the inside of a polymerization vessel of a 500 mL separable flask was replaced with nitrogen, 120 mL of n-hexane (dried by molecular sieves) and 120 mL of chloride were added using a syringe. 80 mL of methylene (dried with molecular sieves) and 0.0876 g (0.38 mmol) of p-dicumyl chloride were added.
After cooling the polymerization vessel in a dry ice / methanol bath at −70 ° C., 0.036 g of 2-methylpyridine was used.
(0.39 mmol) was added. Next, a Teflon liquid sending tube was connected to a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock containing 33.9 mL (419.9 mmol) of the isobutylene monomer, and the isobutylene monomer was sent into the polymerization vessel by nitrogen pressure. Further titanium tetrachloride 1.5
0 mL (13.7 mmol) was added to initiate polymerization.
After stirring at the same temperature for 1 hour from the start of polymerization, about 10 minutes
The reaction was terminated by adding mL of methanol.

After the solvent and the like were distilled off from the reaction solution, it was dissolved in hexane and washed twice with water. Further, a hexane solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain chlorine-terminated polyisobutylene. Mn of the obtained polymer was 7
000, Mw / Mn was 1.16.

[Production Example 2] (Synthesis of chlorine-terminated polyisobutylene) After stirring at the same temperature for 1 hour from the start of polymerization in the same manner as in Production Example 1,
Subsequently, 0.274 g of 1,1-diphenylethylene (1.
(52 mmol) was dissolved and dissolved in 6 mL of n-hexane and 4 mL of methylene chloride, and the mixture was stirred for 10 minutes. Mn of the obtained polymer was 71,000, and Mw / Mn was 1.18.

(Example 1) (Synthesis of α-methylstyrene-isobutylene block copolymer) After purging the polymerization vessel of a 500 mL separable flask with nitrogen, the chlorine-terminated polyisobutylene produced by the method shown in Production Example 1 was used. (23.6 g), and 80 mL of toluene and 120 mL of n-hexane were added using a syringe. The polymerization vessel was cooled by placing it in a dry ice / methanol bath at -70 ° C.
036 g (0.39 mmol) were added. Subsequently, a mixed solution of 12.15 g (102.8 mmol) of α-methylstyrene monomer, 8 mL of toluene, and 12 mL of n-hexane, which had been cooled to −70 ° C. in advance, was added to the polymerization vessel. Further, 1.50 mL of titanium tetrachloride (1
(3.7 mmol) was added to initiate polymerization. Ten minutes after the addition of titanium tetrachloride, about 10 mL of methanol was added to terminate the reaction.

After the solvent and the like were distilled off from the reaction solution, it was dissolved in toluene and washed twice with water. Further, a toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. Mn of the obtained polymer was 9
6,000, Mw / Mn was 1.28.

(Example 2) (Synthesis of indene-isobutylene block copolymer) 5
After replacing the inside of the polymerization vessel of the 00 mL separable flask with nitrogen, chlorine-terminated polyisobutylene (23.6 g) produced by the method shown in Production Example 2 was added, and 120 mL of toluene and 80 mL of n-hexane were added using a syringe. . After cooling the polymerization vessel in a dry ice / methanol bath at −70 ° C., 0.036 g of 2-methylpyridine was used.
(0.39 mmol) was added. Then,-
12.15 g of indene monomer cooled to 70 ° C.
(104.6 mmol), 12 mL of toluene and n-
A mixed solution of 8 mL of hexane was added into the polymerization vessel. Further, 1.50 mL (13.7 mmol) of titanium tetrachloride was added to initiate polymerization. 1 after adding titanium tetrachloride
After 0 minute, about 10 mL of methanol was added to terminate the reaction. After the same treatment as in Example 1, Mn of the obtained polymer was 102,000, and Mw / Mn was 1.30.

Example 3 (Synthesis of Indene-Styrene-Isobutylene Block Copolymer) Indene (2.
43 g, 20.9 mmol) and styrene (9.72 g,
(93.3 mmol), except that a mixed monomer was used. After the same treatment as in Example 1, the resulting polymer had Mn of 105,000 and Mw / Mn of 1.25.

Comparative Example 1 Synthesis of Styrene-Isobutylene Block Copolymer
After the atmosphere in the polymerization vessel of the 00 mL separable flask was replaced with nitrogen, 120 mL of n-hexane (dried by molecular sieve) and 80 mL of methylene chloride (dried by molecular sieve) were added using a syringe.
0.0876 g (0.38 mm)
ol). Dry the polymerization vessel at -70 ° C dry ice /
After cooling in a methanol bath, 0.036 g (0.39 mmol) of 2-methylpyridine was added. Next, 33.9 mL of isobutylene monomer (419.9 mmol)
A leffusion tube made of Teflon was connected to a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock containing l), and an isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. Further, 1.50 mL (13.7 mmol) of titanium tetrachloride was added to initiate polymerization. After stirring at the same temperature for 1 hour from the start of the polymerization, about 1 mL of the polymerization solution was withdrawn from the polymerization solution for sampling. Subsequently, 12.15 g of styrene monomer (11.
6.7 mmol), a mixed solution of 12 mL of n-hexane and 8 mL of methylene chloride was added into the polymerization vessel. Ten minutes after the addition of the mixed solution, about 10 mL of methanol was added to terminate the reaction. After the same treatment as in Example 1, the Mn of the isobutylene polymer before adding styrene was 7
000, Mw / Mn is 1.16, and Mn of the block copolymer after styrene polymerization is 101,000, Mw.
/ Mn was 1.23.

Table 1 shows the Tg, water vapor permeability coefficient and oxygen permeability coefficient of the polymers obtained in Examples 1 to 3 and Comparative Example 1.

Comparative Example 2 Commercially available styrene-ethylene butylene block copolymer (SEBS, Kr manufactured by Shell Chemical Co., Ltd.)
Table 1 shows the Tg, water vapor transmission coefficient, and oxygen transmission coefficient of aton G1650).

[0056]

[Table 1] As is evident from Table 1, the copolymers obtained in the examples have a higher Tg than the block copolymers of the comparative examples, and are excellent in water vapor transmission resistance and gas transmission resistance.

(Example 4) A rubber stopper for medicine was prepared using the polymer obtained in Example 2, and an eluate test (properties, foaming, pH, zinc, When potassium permanganate reducing substance, evaporation residue and ultraviolet absorption spectrum were performed, all of them were suitable. In addition, for the same polymer, according to the Japanese Pharmacopoeia test method for infusion plastic containers, transparency and appearance, dissolution test (properties, foaming, pH, chloride, sulfate, phosphate, ammonium, etc., potassium permanganate, etc.) (Reducing material, evaporation residue, UV absorption spectrum), which also fit.

(Example 5) Using the polymer obtained in Example 1, a tubular sample having an outer diameter of 4 mm was prepared, and the shape after autoclaving under the conditions shown in Table 2 was visually observed. Table 2 shows the results.

Example 6 The same evaluation as in Example 5 was performed using the polymer obtained in Example 2. Table 2 shows the results
Shown in

Example 7 The same evaluation as in Example 5 was performed using the polymer obtained in Example 3. Table 2 shows the results
Shown in

Comparative Example 3 The same evaluation as in Example 5 was performed using the polymer obtained in Comparative Example 1. Table 2 shows the results
Shown in

Comparative Example 4 Commercially available styrene-ethylene butylene block copolymer (SEBS, Kr manufactured by Shell Chemical Co., Ltd.)
atonG1650), and the same evaluations as in Example 5 were performed. Table 2 shows the results.

[0063]

[Table 2] As is clear from Table 2, the polymers obtained in the examples retain their morphology even in sterilization treatment under high temperature conditions, and have excellent heat resistance.

Example 8 Using the polymer obtained in Example 1, the compression set at 70 ° C. for 22 hours and at 100 ° C. for 70 hours were measured in accordance with JIS K-6301. 23 ° C and 70 according to
A tensile test at 0 C was performed. Table 3 shows the results.

Example 9 The same evaluation as in Example 8 was performed using the polymer obtained in Example 2. Table 3 shows the results
Shown in

Example 10 The same evaluation as in Example 8 was carried out using the polymer obtained in Example 3. Table 3 shows the results.

Comparative Example 5 The same evaluation as in Example 8 was carried out using the polymer obtained in Comparative Example 1. Table 3 shows the results
Shown in

Comparative Example 6 A commercially available styrene-ethylenebutylene block copolymer (SEBS, Kr.
atonG1650), and the same evaluations as in Example 8 were performed. Table 3 shows the results.

[0069]

[Table 3] As is clear from Table 3, the polymers obtained in Examples have a small compression set at high temperatures, are excellent as sealable articles under high temperature conditions, and have excellent mechanical strength at high temperatures. I understand.

[0070]

According to the present invention, a novel medical / medical material which is excellent in heat resistance, gas permeability resistance and water vapor permeability and can be used in a wide temperature range, especially in a high temperature range, and a container and a seal made thereof. It is possible to obtain a sexual article.

Claims (13)

[Claims] 1. A polymer block comprising a monomer component (a) containing isobutylene as a main component and an isobutylene block formed from a polymer block containing an aromatic vinyl monomer (b) as a main component. A medical / medical material comprising a polymer, wherein the aromatic vinyl monomer contains at least one selected from the group consisting of α-methylstyrene, p-methylstyrene, vinylnaphthalene derivative and indene derivative. Pharmaceutical and medical materials characterized by the following. 2. The pharmaceutical / medical material according to claim 1, wherein the aromatic vinyl monomer (b) is α-methylstyrene and / or indene. 3. The pharmaceutical / medical material according to claim 1, wherein the aromatic vinyl monomer (b) comprises a mixture of styrene and α-methylstyrene and / or indene. 4. The medicine / medicine according to claim 3, wherein the aromatic vinyl monomer (b) is a mixture of 0 to 95 mol% of styrene and 100 to 5 mol% of α-methylstyrene and / or indene. Materials. 5. The isobutylene-based block copolymer comprises a polymer block containing an aromatic vinyl monomer as a main component, a polymer block containing isobutylene as a main component, and an aromatic vinyl monomer as a main component. Triblock copolymer formed from a polymer block, a polymer block containing an aromatic vinyl monomer as a main component-a diblock copolymer formed from a polymer block containing isobutylene as a main component, or The pharmaceutical / medical material according to claim 1, which is a mixture thereof. 6. The isobutylene-based block copolymer has 5 to 5 polymer blocks mainly composed of an aromatic vinyl-based monomer.
The pharmaceutical / medical material according to claim 1, wherein the material is a block copolymer comprising 80 to 90 parts by weight of a polymer block containing isobutylene as a main component. 7. The isobutylene-based block copolymer has a polymer block containing an aromatic vinyl-based monomer as a main component.
2. The medical / medical material according to claim 1, wherein the polymer block is a block copolymer comprising from 85 to 60 parts by weight of a polymer block containing isobutylene as a main component. 8. The pharmaceutical / medical material according to claim 1, wherein the number average molecular weight of the isobutylene block copolymer is from 30,000 to 500,000. 9. The pharmaceutical / medical material according to claim 1, wherein the number average molecular weight of the isobutylene-based block copolymer is from 50,000 to 400,000. 10. The medicament according to any one of claims 1 to 9,
Container made of medical materials. 11. The medicament according to any one of claims 1 to 9,
Sealable articles made of medical materials. 12. A container comprising a medical / medical material according to claim 10, wherein said container is a medical / medical tube. 13. A sealable article made of a medical or medical material according to claim 11, wherein said sealable article is a medical or medical rubber stopper.