JP2004321788A - Medical member and medical instrument - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a medical member mainly comprising syndiotactic 1, 2-polybutadiene which is useful for medical uses, excellent in flexibility and hardness, has no leak at a joint part, and, further, is also excellent in steam sterilization resistance and to provide a medical instrument obtained by using the member. <P>SOLUTION: The medical member comprises a tube mainly comprising syndiotactic 1, 2-polybutadiene having a crystallinity of not lower than 5% and a connection member connected thereto, the connection member comprising mainly comprising syndiotactic 1, 2-polybutadiene having a crystallinity of not lower than 5% and being at least one selected from a closure-piercing device, a drip chamber, a graduated buret, an air trap, an injection site, a three-way cock and a connector. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a medical member in which a tube mainly composed of syndiotactic 1,2-polybutadiene and a joining member mainly composed of the polybutadiene are connected, and a medical instrument using the same. More specifically, the present invention relates to a medical member mainly composed of syndiotactic 1,2-polybutadiene having excellent flexibility and hardness and also having steam sterilization resistance, and a medical device using the same.

  Syndiotactic 1,2-polybutadiene is a thermoplastic elastomer that has the properties of both plastic (hardness) and rubber (elasticity, flexibility). Since it can be molded into various shapes, it is used for various industrial products. In particular, it has excellent gas permeation resistance and transparency. In addition, compared to vinyl chloride resin, which requires a large amount of plasticizer and has environmental problems such as environmental hormones, it can be molded without adding a plasticizer, and has a moderate flexibility and self-adhesion. Applications to medical applications such as catheters are expanding.

In addition, when syndiotactic 1,2-polybutadiene has a low degree of crystallinity, the melting start temperature is as low as 70 to 90 ° C., and this is used for infusion tubes, infusion containers, and medical devices such as catheters. However, if steam sterilization has poor heat resistance and poses a practical problem, a technique of ethylene oxide gas sterilization has been adopted.
Syndiotactic 1,2-polybutadiene is a method for solving the shortage of performance balance while maintaining the property of being a thermoplastic elastomer having both plastic (hardness) and rubber (elasticity, flexibility) properties. A method has been proposed in which only the surface layer of a molded product is cross-linked and cured by irradiating ultraviolet rays having a given wavelength (Patent Document 1). This method exerts an appropriate effect in terms of improving the performance balance of flexibility, transparency and heat resistance (high-pressure steam sterilization resistance) as a medical member.
JP 2000-129017 A

  In addition, various methods of irradiating an electron beam to obtain a harder surface have been proposed. These methods have a certain effect on scratch resistance.

  However, since the molded product obtained by the method disclosed in the above-mentioned gazette crosslinks only the surface layer by ultraviolet irradiation of a limited region, it is necessary to uniformly crosslink an irregular shape such as a tube. Is difficult. In addition, the heat resistance of the inside of the medical tube is not always sufficiently satisfactory. When the tube is subjected to a general high-pressure steam sterilization treatment (121 ° C. × 20 minutes), the inside of the insufficiently crosslinked tube is melted. This may cause unevenness in the thickness of the tube, that is, unevenness in the hardness of the tube. On the other hand, the conventional method using an electron beam has a problem that the inside of a molded product is excessively hardened, and flexibility, which is one property of syndiotactic 1,2-polybutadiene, is almost lost. is there.

  In addition, a medical instrument such as an infusion set is configured by, for example, joining the medical tube and a joining member. As described above, from the viewpoint of plasticizer-free, when 1,2-polybutadiene is used for a medical tube, heat resistance is insufficient, or a bonding member is generally made of an olefin resin such as polypropylene or a polycarbonate resin. Is adopted, adhesion to a dissimilar material occurs, and as a result, the bonding strength between the tube and the bonding member is insufficient, and liquid leakage or the like is likely to occur.

  The present invention has been made in view of the above-described problems, and is syndiotactic, which is useful for medical applications, has excellent flexibility and hardness, has no liquid leakage at a joint portion, and further has excellent steam sterilization resistance. An object is to provide a medical member mainly composed of 1,2-polybutadiene and a medical device using the same.

The present invention relates to a tube mainly composed of syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more and a joining mainly composed of syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more. The present invention relates to a medical member connected to a member.
Here, the joining member is not particularly limited, and includes, for example, at least one selected from a bottle needle, a drip tube, a scale tube, an octopus tube, a mixed injection rubber, a three-way cock, and a connector.
In addition, the phrase “mainly composed of syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more” that constitutes the tube and the joining member includes not only the use of syndiotactic 1,2-polybutadiene alone but also the use of syndiotactic 1,2-polybutadiene alone. , (A) 100 to 60 parts by mass of syndiotactic 1,2-polybutadiene, and (B) polyethylene, polypropylene, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) ), Hydrides thereof (SEBS, SEPS), polybutadienes (BR) other than the above-mentioned syndiotactic 1,2-polybutadiene, ABS resin, polyisoprene, various polyethylenes (LLDPE, ULDPE, LDPE), ethylene-vinyl acetate copolymer, Ethylene-acrylate ester Copolymers, and ethylene - may be a composition comprising at least one other thermoplastic polymer 0-40 parts by weight selected from the group consisting of methacrylic acid copolymer.
In the medical member of the present invention, the tube and the joining member are connected by solvent bonding, ultrasonic bonding, or high-frequency bonding.
Furthermore, the medical member of the present invention includes those that can be steam-sterilized.
Furthermore, in the medical member of the present invention, the tube is preferably cross-linked by an electron beam.
Furthermore, the medical member of the present invention preferably has a halogen content of 200 ppm or less.
Further, the medical member of the present invention may contain 10 parts by mass or less of a lubricant with respect to 100 parts by mass of the resin component mainly composed of syndiotactic 1,2-polybutadiene.
Next, the present invention relates to a medical device including the medical member as a constituent element.

  According to the present invention, useful for medical applications, while being excellent in flexibility and hardness, excellent in steam sterilization resistance, furthermore, without leakage at the joint, recyclable, and further containing no vinyl chloride resin It is possible to provide a medical member mainly composed of syndiotactic 1,2-polybutadiene and a medical device using the same, which are friendly to environmental problems.

  The connector having the tube or tube connecting portion of the present invention includes (A) syndiotactic 1,2-polybutadiene alone or (A) syndiotactic 1,2-polybutadiene and (B) another thermoplastic polymer. Is used. This (A) syndiotactic 1,2-polybutadiene is a syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more, preferably 10 to 40%, and its melting point is preferably It is in the range of 50 to 150 ° C, more preferably 60 to 140 ° C. When the crystallinity / melting point is in this range, the result is excellent in balance between mechanical strength such as tensile strength and tear strength and flexibility.

Note that syndiotactic 1,2-polybutadiene having a crystallinity of up to about 5 to 25% by mass (hereinafter, also referred to as “low-crystal RB”) has excellent flexibility and is used as a tube body. However, since the low crystallinity RB has a low melting point (melting point = about 70 to 95 ° C), it has poor steam sterilization resistance. For this reason, as described later, it is desirable to impart heat resistance by cross-linking by electron beam irradiation.
On the other hand, the syndiotactic 1,2-polybutadiene having a crystallinity of about 25 to 40% by mass (hereinafter also referred to as “highly crystalline RB”) has a relatively high melting point (melting point = about 105 to 140 ° C.). In the present invention, it is preferable to use as a joining member, rather than as a tube, because of its high hardness and poor flexibility.

  The (A) syndiotactic 1,2-polybutadiene used in the present invention has, for example, a 1,2-bond content of 70% or more, and for example, contains a catalyst containing a cobalt compound and an aluminoxane. Below, it is obtained by polymerizing butadiene, but is not limited to this production method.

  The 1,2-bond content in the butadiene-bonding unit of the (A) syndiotactic 1,2-polybutadiene used in the present invention is usually at least 70%, preferably at least 80%, more preferably at least 90%. . When the 1,2-bond content is 70% by mass or more, the 1,2-polybutadiene exhibits excellent properties as a thermoplastic elastomer.

In the (A) syndiotactic 1,2-polybutadiene used in the present invention, a small amount of a conjugated diene other than butadiene may be copolymerized. Examples of the conjugated diene other than butadiene include 1,3-pentadiene, 1,3-butadiene derivatives substituted with a higher alkyl group, and 2-alkyl-substituted-1,3-butadiene.
Among them, 1,3-butadiene derivatives substituted by higher alkyl groups include 1-pentyl-1,3-butadiene, 1-hexyl-1,3-butadiene, 1-heptyl-1,3-butadiene, -Octyl 1,3-butadiene and the like.

  Here, typical examples of 2-alkyl-substituted-1,3-butadiene include 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3-butadiene, and 2-propyl-1,3. -Butadiene, 2-isopropyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-isobutyl-1,3-butadiene, 2-amyl-1,3-butadiene, 2-isoamyl-1,3 -Butadiene, 2-hexyl-1,3-butadiene, 2-cyclohexyl-1,3-butadiene, 2-isohexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-isoheptyl-1,3 -Butadiene, 2-octyl-1,3-butadiene, 2-isooctyl-1,3-butadiene and the like. Among these conjugated dienes, preferred conjugated dienes copolymerized with butadiene include isoprene and 1,3-pentadiene. The content of butadiene in the monomer component used for the polymerization is preferably at least 50 mol%, particularly preferably at least 70 mol%.

  As described above, (A) the syndiotactic 1,2-polybutadiene used in the present invention is obtained, for example, by polymerizing butadiene in the presence of a catalyst containing a cobalt compound and an aluminoxane. As the cobalt compound, preferably, an organic acid salt of cobalt having 4 or more carbon atoms can be exemplified. Specific examples of the organic acid salt of cobalt include octylate such as butyrate, hexanoate, heptylate and 2-ethyl-hexyl acid, decanoate, and higher grades such as stearic acid, oleic acid and erucic acid. Examples thereof include fatty acid salts, benzoates, tolylates, xylylates, alkyls such as ethylbenzoic acid, aralkyl, allyl-substituted benzoates and naphthoates, and alkyl, aralkyl or allyl-substituted naphthoates. Of these, the so-called octylates of 2-ethylhexylic acid, stearates, and benzoates are preferred because of their excellent solubility in hydrocarbon solvents.

  Examples of the aluminoxane include those represented by the following general formula (I) or (II).

  In the aluminoxane represented by the general formula (I) or (II), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and is preferably a methyl group or an ethyl group; Particularly preferred is a methyl group. M is an integer of 2 or more, preferably 5 or more, and more preferably 10 to 100. Specific examples of the aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane and the like, and methylaluminoxane is particularly preferred.

  It is extremely preferable that the polymerization catalyst contains a phosphine compound in addition to the above-mentioned cobalt compound and aluminoxane. The phosphine compound is a component effective for activating the polymerization catalyst and controlling the vinyl bond structure and crystallinity, and preferably includes an organic phosphorus compound represented by the following general formula (III).

P (Ar) _n (R ') _3-n ... (III)
In the general formula (III), Ar represents a group shown below.

(In the above groups, R ¹ , R ² , and R ³ are the same or different and are a hydrogen atom, an alkyl group having preferably 1 to 6 carbon atoms, a halogen atom, an alkoxy group having preferably 1 to 6 carbon atoms or It preferably represents an aryl group having 6 to 12 carbon atoms.)
In the general formula (III), R ′ represents a cycloalkyl group or an alkyl-substituted cycloalkyl group, and n is an integer of 0 to 3.

  Specific examples of the phosphine compound represented by the general formula (III) include tri- (3-methylphenyl) phosphine, tri- (3-ethylphenyl) phosphine, tri- (3,5-dimethylphenyl) phosphine, Tri- (3,4-dimethylphenyl) phosphine, tri- (3-isopropylphenyl) phosphine, tri- (3-t-butylphenyl) phosphine, tri- (3,5-diethylphenyl) phosphine, tri- (3 -Methyl-5-ethylphenyl) phosphine), tri- (3-phenylphenyl) phosphine, tri- (3,4,5-trimethylphenyl) phosphine, tri- (4-methoxy-3,5-dimethylphenyl) phosphine , Tri- (4-ethoxy-3,5-diethylphenyl) phosphine, tri- (4-butoxy-3,5-di Butylphenyl) phosphine, tri (p- methoxyphenyl) phosphine, tricyclohexylphosphine, dicyclohexylphenylphosphine, tribenzylphosphine, tri (4-methylphenyl) phosphine, tri (4-ethylphenyl) phosphine and the like. Of these, particularly preferred are triphenylphosphine, tri- (3-methylphenyl) phosphine, tri- (4-methoxy-3,5-dimethylphenyl) phosphine and the like.

  Further, as the cobalt compound, a compound represented by the following general formula (IV) can be used.

  The compound represented by the general formula (IV) is a complex having, as a ligand, a phosphine compound in which n is 3 in the general formula (III) with respect to cobalt chloride. When using this cobalt compound, a compound synthesized in advance may be used, or a method in which cobalt chloride and a phosphine compound are brought into contact in a polymerization system may be used. By selecting various phosphine compounds in the complex, it is possible to control the amount of 1,2-bonds and the crystallinity of the resulting syndiotactic 1,2-polybutadiene.

  Specific examples of the cobalt compound represented by the general formula (IV) include cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride, and cobalt bis [tris (3-ethylphenyl). Phosphine)] dichloride, cobalt bis [tris (4-methylphenylphosphine)] dichloride, cobalt bis [tris (3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (3,4-dimethylphenylphosphine)] dichloride , Cobalt bis [tris (3-isopropylphenylphosphine)] dichloride, cobalt bis [tris (3-t-butylphenylphosphine)] dichloride, cobalt bis [tris (3,5-diethylphenylphosphine)] Dichloride, cobalt bis [tris (3-methyl-5-ethylphenylphosphine)] dichloride, cobalt bis [tris (3-phenylphenylphosphine)] dichloride, cobalt bis [tris (3,4,5-trimethylphenylphosphine)] Dichloride, cobalt bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (4-ethoxy-3,5-diethylphenylphosphine)] dichloride, cobalt bis [tris (4-butoxy) -3,5-dibutylphenylphosphine)] dichloride, cobalt bis [tris (4-methoxyphenylphosphine)] dichloride, cobalt bis [tris (3-methoxyphenylphosphine)] dichloride, cobalt bis [tri [4- (dodecylphenylphosphine)] dichloride, cobalt bis [tris (4-ethylphenylphosphine)] dichloride and the like can be used.

  Of these, particularly preferred are cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride, cobalt bis [tris (3,5-dimethylphenylphosphine)] dichloride, Bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride;

The amount of the catalyst to be used is as follows. In the case of homopolymerization of butadiene, butadiene is used in an amount of 0.1 mol per mol of butadiene. In the case of copolymerization, the amount of the cobalt compound is 0.1 mol per mol of the total amount of butadiene and conjugated diene other than butadiene. It is used in an amount of about 001 to 1 mmol, preferably about 0.01 to 0.5 mmol. The amount of the phosphine compound to be used is generally 0.1 to 50, preferably 0.5 to 20, more preferably 1 to 20, as a ratio of phosphorus atoms to cobalt atoms (P / Co). Further, the amount of aluminoxane used is usually 4 to 10 ⁷ , preferably 10 to 10 ⁶ as a ratio of aluminum atom to cobalt atom (Al / Co) of the cobalt compound. In the case where the complex represented by the general formula (IV) is used, the amount of the phosphine compound used is such that the ratio of the phosphorus atom to the cobalt atom (P / Co) is 2, and the amount of the aluminoxane is as described above. According to the description.

  As the inert organic solvent used as the polymerization solvent, for example, benzene, toluene, xylene, aromatic hydrocarbon solvents such as cumene, n-pentane, n-hexane, aliphatic hydrocarbon solvents such as n-butane, cyclopentane, Alicyclic hydrocarbon solvents such as methylcyclopentane and cyclohexane, and mixtures thereof.

The polymerization temperature is usually from -50 to 120C, preferably from -20 to 100C.
The polymerization reaction may be a batch type or a continuous type. The concentration of the monomer in the solvent is usually 5 to 50% by mass, preferably 10 to 35% by mass.
In addition, in order to prevent the deactivation of the catalyst and the polymer of the present invention in producing the polymer, consideration should be given to minimizing the incorporation of a compound having a deactivating effect such as oxygen, water or carbon dioxide gas into the polymerization system. is necessary. When the polymerization reaction has progressed to the desired stage, the reaction mixture is added with alcohol, other polymerization terminators, antioxidants, antioxidants, ultraviolet absorbers, etc., and then the produced polymer is separated, washed and dried according to the usual method. Thus, the syndiotactic 1,2-polybutadiene used in the present invention can be obtained.

  The weight average molecular weight of the (A) syndiotactic 1,2-polybutadiene used in the present invention is preferably 10,000 to 5,000,000, more preferably 10,000 to 1.5,000,000, and particularly preferably 50,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the fluidity is extremely high, processing becomes extremely difficult, and the molded product (medical member) is not sticky, and if it exceeds 5,000,000, the fluidity is extremely low, Processing becomes very difficult, which is not preferable.

  On the other hand, the thermoplastic polymer (B) is a thermoplastic resin and / or a thermoplastic elastomer other than the component (A). Specifically, polyethylene, polypropylene, styrene-butadiene-styrene block copolymer (SBS) ), Styrene-isoprene-styrene block copolymer (SIS), hydrides thereof (SEBS, SEPS), polybutadiene (BR) other than the above-mentioned syndiotactic 1,2-polybutadiene, ABS resin, polyisoprene, various polyethylenes ( LLDPE, ULDPE, LDPE), ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, and ethylene-methacrylic acid copolymer.

  The compounding amount of the component (B) is 40 parts by mass or less, preferably 0 to 35 parts by mass, per 100 parts by mass of the total amount of the components (A) and (B). When the amount exceeds 40 parts by mass, the proportion of the component (A) used is reduced, and the original flexibility of the component (A) is lost.

The composition used in the present invention may contain additives such as a lubricant, a filler or a foaming agent, if necessary, in addition to the components (A) and (B). Specific examples of the above additives include lubricants such as paraffin oil, silicone oil, liquid polyisoprene, liquid polybutadiene, erucamide, stearamide, talc, silica, magnesium hydroxide, calcium carbonate, glass, and carbon fiber. , A filler such as a glass balloon, and a foaming agent such as microspheres, ADCA, OBSH, baking soda, and AIBN manufactured by Matsumoto Yushi Co., Ltd.
In addition, the usage-amount of a lubricant is 10 mass parts or less, Preferably it is 0.01-8 mass parts with respect to resin component, ie, 100 mass parts of total of (A)-(B) component. If it exceeds 10 parts by mass, the lubricant bleeds out of the product and elutes in the used drug, which is not preferable.

  Further, in order to improve the balance between heat resistance and flexibility by electron beam irradiation, other additives, for example, a polyfunctional monomer such as trimethylpropane trimethacrylate, a photopolymerization initiator such as hydroxycyclohexyl phenyl ketone, benzophenone and the like May be contained in an amount of 5 parts by mass or less based on 100 parts by mass of syndiotactic 1,2-polybutadiene.

Preparation of Composition and Molding The composition used in the present invention is obtained by adding the above component (A) alone or the components (A) to (B), and if necessary, the above additives. It is softened by heating, kneaded and molded. The kneading and molding are carried out in a temperature range in which the syndiotactic 1,2-polybutadiene has a good moldability from the softening temperature to the melting temperature or higher to obtain a homogeneous molded article (medical member). For this reason, the molding temperature is preferably about 90 to 170 ° C. In order to obtain molded products such as tubes and connectors, press molding, extrusion molding, injection molding, blow molding, profile extrusion molding, T-die film molding, inflation molding, powder slush molding, rotational molding, etc. are used, and tubes and joints are used. It is molded into a member.

Electron Beam Irradiation Among the medical members of the present invention, a tube requires flexibility, and therefore low-crystal RB is used. However, since the melting point is low, the tube is irradiated with an electron beam in order to exhibit steam sterilization resistance. And can be crosslinked. When irradiated with an electron beam, the vinyl group of the syndiotactic 1,2-polybutadiene undergoes a radical polymerization to form a three-dimensional crosslinked structure, which cures the molded article (tube) and imparts heat resistance. The electron beam is permeable to the synthetic resin, and the degree of the transmission depends on the thickness of the molded product and the kinetic energy of the electron beam.
When the energy of the electron beam is adjusted so that it can be transmitted uniformly in the thickness direction according to the irradiation thickness, a molded article (tube) having a uniform degree of crosslinking in the thickness direction can be obtained.
The connector may be irradiated with an electron beam.
The electron beam irradiation may be performed before or after bonding the tube and the connector.

  The energy of the electron beam is preferably from 50 to 3,000 kV, more preferably from 300 to 2,000 kV with respect to the above medical member. Is relatively large, so that the number of electron beams transmitted through the medical member decreases, and the internal crosslinking is delayed as compared with the surface layer portion, resulting in a difference in the degree of crosslinking. On the other hand, if it is larger than 3,000 kV, the degree of crosslinking becomes too large and becomes hard, which is not preferable because elasticity and elongation are small.

  The irradiation amount of the electron beam at this time is preferably from 1 to 100 Mrad (corresponding to 10 to 1,000 kGy in SI unit system), and more preferably from 1 to 50 Mrad for crosslinking and curing. If it is less than 1 Mrad, the degree of crosslinking of 1,2-polybutadiene is small, while if it exceeds 100 Mrad, the degree of crosslinking becomes too large and becomes hard, which is not preferable because elasticity and elongation are small.

  Crosslinking by electron beam irradiation can be represented by the product of electron beam energy and irradiation dose. In the present invention, the product of electron beam acceleration voltage (kV) and irradiation dose (Mrad) is preferably 2,000 to 20 5,000 (kV · Mrad), more preferably 5,000 to 16,000 (kV · Mrad). If it is smaller than 2,000 (kV · Mrad), the ratio of electrons captured and absorbed in the surface layer portion becomes relatively large, so that the number of electron beams transmitted through the medical member decreases, and the inside of the medical member decreases. It is not preferable because crosslinking is delayed and a difference occurs in the degree of crosslinking. On the other hand, if it is larger than 20,000 (kV · Mrad), the degree of cross-linking becomes too large and becomes hard, so that the elasticity and elongation are small.

By subjecting the medical member of the present invention to the above-mentioned electron beam irradiation, the elastic modulus (M2 ₅₀ ) of the medical member after the electron beam irradiation at 50% elongation is increased at the 50% elongation before the electron beam irradiation. The ratio (M1 ₅₀ ) can be preferably 1.1 to 2.5 times, more preferably 1.1 to 2.0 times. When M2 ₅₀ / M1 ₅₀ is less than 1.1, electron beam crosslinking is not advanced, and the steam sterilization resistance is poor. On the other hand, when it exceeds 2.5, the crosslinked medical member becomes too hard and flexible. Is not preferred. M2 ₅₀ / M1 ₅₀ is the product of the electron beam acceleration voltage (kV) and irradiation dose (Mrad), by a 2,000~20,000 (kV · Mrad), it can be easily adjusted.

Moreover, the crosslinked medical member obtained after electron beam irradiation obtained in this manner has steam sterilization resistance. For example, using the crosslinked infusion tube of the present invention, the crosslinked medical member is heated at 100 to 121 ° C for 10 to 10 minutes. There is no deformation even after steam sterilization for about 20 minutes.
Here, the term “steam sterilization resistance” refers specifically to high-pressure steam sterilization of a resin molded product such as an infusion tube (for example, a tube having an inner diameter of 3 mmφ, an outer diameter of 4.4 mmφ, a wall thickness of 0.7 mm, and a tube length of 20 cm). When placed in a vessel and steam sterilized at 121 ° C. for 20 minutes, the circle before sterilization is maintained, meaning that no deformation is observed.

  Further, the haze value of the medical member irradiated with the electron beam of the present invention is preferably 30 or less, more preferably 25 or less. The haze value is a measure of transparency, the smaller the value, the better the transparency. This haze value was measured according to ASTM D-1003.

Further, in the medical member of the present invention after electron beam irradiation, the toluene-insoluble content is usually 50 to 99% by mass, preferably 80 to 95% by mass. The toluene-insoluble matter is a barometer that indicates to what extent double bonds in (A) syndiotactic 1,2-polybutadiene are crosslinked by irradiating the medical member with an electron beam.
Here, the toluene-insoluble matter is obtained by immersing the medical member [(a) g] of the present invention in 100 ml of toluene, leaving it to stand at 30 ° C. for 48 hours, and then filtering it using a 100-mesh wire mesh, and a part of the filtrate. After [(c) ml] was collected, it was evaporated to dryness and solidified, and the obtained residual solid content [toluene-soluble component: (b) g] was weighed, and the gel content was calculated by the following equation.
Gel content (% by mass) = [{ab × (100 / c)} / a] × 100
When the toluene-insoluble content is less than 50% by mass, crosslinking by electron beam irradiation is insufficient, heat resistance is poor, and steam sterilization resistance is poor. On the other hand, if it exceeds 99% by mass, the crosslinking by electron beam irradiation proceeds too much, and the medical member becomes too hard, and the flexibility is lost, which is not preferable.
The toluene insoluble content can be easily adjusted by setting the product of the electron beam acceleration voltage (kV) and the irradiation dose (Mrad) to 2,000 to 20,000 (kV · Mrad).

  Further, the medical member of the present invention has a halogen atom content of preferably 200 ppm or less, more preferably 100 ppm or less. The content of the halogen atom is, for example, as described above, by using a non-halogen inert organic solvent as a polymerization solvent, the content of the halogen atom in the obtained 1,2-polybutadiene is preferably 200 ppm or less. , More preferably 100 ppm or less. It is preferable to use only a non-halogen compound in the catalyst system because the content of halogen atoms in the medical member can be further reduced.

Next, an infusion set using the medical member of the present invention will be described more specifically with reference to FIG.
The infusion set 10 includes a bottle needle 14 having a tube joint 15 for infusion discharge in an infusion bag 12, a first tube C <b> 1 connecting the bottle needle 14 drip tube 11, a drip tube 11 and a puncture needle 13. , A connector 19 for coupling the second tube C2 and the puncture needle 13, a clamp 18 for adjusting the infusion rate, and a cap 16 for enclosing the puncture needle 13. Have.

Here, as the puncture needle 13, a metal needle made of hollow stainless steel or the like having a puncture blade at the tip, or a synthetic resin needle is used. Further, a roller clamp is used as the clamp 18, and the roller clamp includes a roller 17 movably provided, and the roller 17 moves toward the puncture needle 13 to flow through the second tube C2. The route becomes narrower and the infusion rate can be adjusted. A filter (not shown) is accommodated in the drip tube 11 in case a foreign substance is included in the infusion solution or the like. In addition, as the puncture needle 13, a conventionally used one is used.
Further, in the present invention, the bottle needle 14, the drip tube 11, and the connector 19 having the tube connecting portion 15 all correspond to the connecting member defined in the present invention, and have a crystallinity of 5% or more, preferably a crystal. Syndiotactic 1,2-polybutadiene having a high degree of crystallization of about 25 to 40% is used.

  Further, as the tubes C1 and C2, soft tubes having transparency are suitable. Specifically, a conventional soft vinyl chloride resin and a conventional low-crystallinity syndite having a crystallinity of about 5 to 25% are used. An electron beam cross-linking of the syndiotactic 1,2-polybutadiene of the present invention having a low crystallinity of 5% or more, preferably about 5 to 25%, instead of the tactic 1,2-polybutadiene. Is used.

In addition, the joining members of the bottle needle 14, the drip tube 11, and the connector 19 each having the tube joining portion 15 and the distal end of each of the tubes C1 and C2 are tightly fixed by solvent bonding, ultrasonic bonding, or high frequency bonding.
In the present invention, since both the tube and the joining member are made of syndiotactic 1,2-polybutadiene, they can be fixed firmly and firmly without liquid leakage.
Here, examples of the solvent adhesion include tetrahydrofuran, cyclohexane, and toluene.
In addition to the solvent, bonding by an adhesive, ultrasonic wave, high frequency, or the like may be used.

  In the present invention, the medical member including the tube and the joining member can be applied as a component of the above-described infusion set and a component of a medical device such as a drug administration catheter.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In the examples, parts and% are based on mass unless otherwise specified. In addition, various measurements in the examples were performed according to the following.

Reference Example 1
The following tubes were used.
Tube A-1: RB with a crystallinity of 18% (JSR RB810, manufactured by JSR)
Tube A-2: Blend of RB (JSR RB820 manufactured by JSR) having a crystallinity of 24% and SIS (styrene-isoprene-styrene block copolymer, JSR SIS5229P manufactured by JSR) (mass ratio = 70/30) )
Tube A-3: Electron beam (EB) irradiation product of A-1 product (500 kV × 5 Mrad)
Tube A-4: A-2 product electron beam (EB) irradiation product (500 kV × 5 Mrad)
Tube a-1: 100 parts of LLDPE (manufactured by Tosoh Corporation, LUMITAC 24-1) blended with 15 parts of a plasticizer (liquid paraffin).
Tube a-2: flexible PVC [Daichi PVC SX-13 manufactured by Sumitomo Chemical Co., Ltd. (containing 60 phr of DOP)]
The dimensions of the tubes are 3 mm in inner diameter, 4.4 mm in outer diameter, 0.7 mm in wall thickness, and 20 cm in tube length.
Table 1 shows the properties of each tube.

Reference Example 2
The following were used as connectors.
Connector B-1: RB840 (syndiotactic 1,2-polybutadiene having a crystallinity of 34%) manufactured by JSR Corporation
Connector B-2: RB-irradiated product of RB840 (500 kV × 5 Mrad)
Connector B-3: RB830 (syndiotactic 1,2-polybutadiene having a crystallinity of 28%) manufactured by JSR Corporation
Connector b-1: polypropylene resin for injection molding (manufactured by Tosoh Corporation, Polypro J5080Q)
Connector b-2; polycarbonate resin for injection molding (Panlite K-1285J, manufactured by Teijin Chemicals Limited)
Connector b-3: PVC for injection molding (Daichi PVC SX-8G, manufactured by Sumitomo Chemical Co., Ltd.)
Table 1 shows the properties of each connector.

The dimensions of the connector and the tube are as follows.
Connector: Bonded part outside diameter 3.7mmφ, bonded part length 1cm
Tube: 3.0mm inside diameter
FIG. 2 schematically shows the connector and the tube. FIG. 2A is a schematic diagram of a connector, and FIG. 2B is a schematic diagram of a tube.

Halogen content:
Those having a halogen content of 200 ppm or less were evaluated as ○, and those having a halogen content exceeding 200 ppm were evaluated as x.
Plasticizer:
Those containing no plasticizer were evaluated as ○, and those containing plasticizer were evaluated as x.

Examples 1 to 12, Comparative Examples 1 to 24
By combining the tube of Reference Example 1 and the connector used in Comparative Example 2, a medical member was prepared. 1. solvent adhesion; 2. Steam sterilization resistance; EOG sterilization resistance was evaluated respectively. Table 2 shows the results.

1. Solvent adhesion:
Using cyclohexane as a solvent, the tube and the connector were solvent-bonded. Bend the end of the tube opposite to the bonded part and fix it with clips. Send compressed air (0.3 MPa) from the connector side. Good air leakage from the bonded part (observed in water) (○) Those with air leakage were evaluated as defective (x).
2. Steam sterilization resistance:
After steam sterilization (121 ° C. × 20 minutes), those having no shape change were evaluated as ○, and those having changed were evaluated as x.
3. EOG sterilization resistance:
After EOG (ethylene oxide gas) sterilization (60 ° C. × 120 minutes), those having no shape change were evaluated as ○, and those having changed were evaluated as x.

  The medical member of the present invention is useful for medical applications, is excellent in flexibility and hardness, is excellent in steam sterilization resistance, is free of liquid leakage at the joint, is recyclable, and does not contain a vinyl chloride resin. Therefore, the present invention is useful for a medical member mainly composed of syndiotactic 1,2-polybutadiene and a medical device using the same, which is friendly to environmental problems.

It is a top view of the infusion set which comprises the medical member of this invention as a component. (A) is a schematic diagram of a connector, (b) is a schematic diagram of a tube.

Explanation of reference numerals

Reference Signs List 10 infusion set 11 infusion tube 12 infusion bag 13 puncture needle 14 bottle needle 15 tube connection part 18 clamp 19 connector C1-C2 tube

Claims (8)

  A tube mainly composed of syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more is connected to a joining member mainly composed of syndiotactic 1,2-polybutadiene having a crystallinity of 5% or more. Medical parts.   The medical member according to claim 1, wherein the joining member is at least one selected from a bottle needle, a drip tube, a scale tube, an octopus tube, a mixed injection rubber, a three-way cock, and a connector.   The medical member according to claim 1, wherein the tube and the joining member are connected by solvent bonding, ultrasonic bonding, or high-frequency bonding.   The medical member according to any one of claims 1 to 3, which can be steam-sterilized. The medical member according to any one of claims 1 to 4, wherein the tube is cross-linked with an electron beam.   The medical member according to any one of claims 1 to 5, wherein the halogen content is 200 ppm or less.   The medical member according to any one of claims 1 to 6, wherein the lubricant is contained in an amount of 10 parts by mass or less based on 100 parts by mass of the resin component mainly composed of syndiotactic 1,2-polybutadiene. A medical device comprising the medical member according to any one of claims 1 to 7.

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