JP2001120655A - Method for manufacturing catheter, and catheter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catheter excellent in flexibility, transparency and thermoplasticity, and a method for manufacturing the same. SOLUTION: A catheter is manufactured by using an olefin resin and a resin composition consisting of a hydrogenated matter of a block copolymer consisting of a polymer block consisting of one or more vinyl aromatic compound and a polymer block consisting of one or more conjugated diene compound. In this manufacturing method, after a resin composition is extrusion-molded, heating and cooling are repeated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a catheter and a catheter. More specifically, a resin composition comprising an olefin-based resin and a block copolymer hydrogenated product comprising a polymer block comprising one or more vinyl aromatic compounds and a polymer block comprising one or more conjugated diene compounds. The present invention relates to a method for producing a catheter using the same and a catheter obtained by the method. The catheter obtained by the production method of the present invention is excellent in transparency, heat resistance, heat setting property and heat processing property, and thus is suitably used as a catheter for respiratory systems, intravascular use, and the like.

[0002]

2. Description of the Related Art Since a catheter is required to have excellent flexibility and transparency, it is often manufactured using soft vinyl chloride, which is a material having both of these properties. However, soft vinyl chloride is DOP
A relatively large amount of a low molecular weight plasticizer such as (dioctyl phthalate) is added, and the problem of elution of the plasticizer has been pointed out from the viewpoint of safety. In recent years, disposable medical devices have been promoted and are obliged to be incinerated after use.However, medical devices using soft vinyl chloride generate toxic gas when incinerated,
There is a problem of causing environmental pollution. In addition, sterilization of a catheter made of soft vinyl chloride is generally performed with ethylene oxide gas, and there is a concern that the residual gas may adversely affect a patient. Autoclave sterilization (high-pressure steam sterilization) is used to eliminate the effects of residual gas.
However, soft vinyl chloride has poor heat resistance,
It cannot withstand this sterilization method.

For this reason, recently, conversion of soft vinyl chloride to another material as a material for medical devices has been studied. Japanese Patent Application Laid-Open No. 4-159344 discloses olefin resins, hydrogenated styrene-butadiene block copolymers, and styrene-isoprene blocks. A resin composition comprising a hydrogenated copolymer has been proposed.
JP-A-10-67894 proposes a resin composition comprising a polypropylene resin and a hydrogenated product of a styrene-butadiene block copolymer and / or a hydrogenated product of a styrene-isoprene block copolymer. I have.

[0004]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 4-159.
The resin composition described in Japanese Patent No. 344 or 344 gives a molded article having excellent flexibility and contains no chlorine or nitrogen.
It has the characteristic that no toxic gas is generated when the molded product is completely burned. However, when a molded article obtained from such a resin composition is used as a medical device such as a catheter, the properties required for the medical device, that is, transparency, heat resistance, heat-setting property and heat-processability are not sufficiently satisfactory. Rather, there is room for improvement, particularly in this regard, in catheters. Therefore, an object of the present invention is to provide a method of manufacturing a catheter excellent in transparency, heat resistance, heat setting property, and heat processing property, and a catheter.

[0005]

Means for Solving the Problems The present inventors have intensively studied and studied a polymer comprising an olefin resin, a polymer block comprising at least one vinyl aromatic compound and at least one conjugated diene compound. The present inventors have found that a catheter suitable for the above-mentioned purpose can be manufactured by repeatedly heating and cooling after extruding a resin composition comprising a block copolymer hydrogenated product consisting of blocks, and have reached the present invention.

That is, the present invention relates to a hydrogenated block copolymer comprising an olefin resin, a polymer block comprising at least one vinyl aromatic compound and a polymer block comprising at least one conjugated diene compound. A method for producing a catheter using a resin composition comprising: extruding the resin composition; and repeating heating and cooling.

Another invention of the present invention is directed to a block copolymer water comprising an olefin resin, a polymer block comprising at least one vinyl aromatic compound and a polymer block comprising at least one conjugated diene compound. This is a catheter obtained by repeatedly heating and cooling after extruding a resin composition comprising an additive.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin resin used in the present invention includes polyethylene such as high-density polyethylene and low-density polyethylene, polypropylene and a resin containing these as a main component, and a propylene resin is preferred. Hereinafter, the olefin resin used in the present invention is referred to as an olefin resin (a). The polypropylene resin may be any of homopolypropylene, random polypropylene and block polypropylene. Also,
The polypropylene resins may be used alone or in combination of two or more. The melt viscosity of the polypropylene resin is 230 ° C. according to ASTM D-1238,
The melt flow rate (MFR) measured at a load of 2160 g is preferably in the range of 0.1 to 500, more preferably in the range of 2 to 200.

The vinyl aromatic compound used in the present invention includes styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, Ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like can be mentioned, and among them, styrene is preferable. The number average molecular weight of the polymer block composed of a vinyl aromatic compound (hereinafter, sometimes referred to as polymer block A) is not particularly limited, but may be 2,50.
It is preferably in the range of 0 to 20,000.

The conjugated diene compound in the block copolymer hydrogenated from the polymer block composed of the conjugated diene compound used in the present invention includes isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene. , 1,3-pentadiene and the like. Of these, isoprene and butadiene are preferred.

The hydrogenated block copolymer having an isoprene polymer block has a content of 1,2 bonds and 3,4 bonds (hereinafter, simply referred to as vinyl bonds) of from 10 to 75.
%. When the content of the vinyl bond is less than 10%, the transparency of the catheter obtained from the resin composition may be insufficient, and when it exceeds 75%, the glass transition temperature (Tg) becomes too high, The heat setting of the catheter may be impaired. Further, it is preferable that 70% or more of the carbon-carbon double bond in the isoprene polymer block is hydrogenated. When the hydrogenation ratio is less than 70%, the weather resistance and the heat resistance may be poor, and the catheter obtained from the resin composition may be deteriorated during use. Further, the compatibility with the polypropylene resin tends to be poor, and the transparency may be impaired. In addition, the heat setting property is that, after extrusion molding of the resin composition, heating and cooling are repeated,
A property that is fixed in a predetermined shape and does not easily return to the initial shape. The number average molecular weight of the isoprene polymer block (hereinafter sometimes referred to as polymer block B) is not particularly limited, but is preferably in the range of 10,000 to 200,000.

The hydrogenated block copolymer having an isoprene / butadiene polymer block is a copolymer comprising isoprene and butadiene in a weight ratio of 5/95 to 95/5, and having a vinyl bond content of It is preferably in the range of 20 to 85%, and more than 70% of carbon-carbon double bonds are hydrogenated. When the isoprene content exceeds 95% by weight, the vinyl bond content is 75%.
In such a case, the glass transition temperature (Tg) becomes too high, and the heat setting property of the catheter may be impaired. On the other hand, when the content of isoprene is less than 5% by weight, when the vinyl bond content is less than 30%, the transparency of the catheter may decrease.

In the isoprene / butadiene polymer block, if the vinyl bond content is less than 20%, the transparency of the catheter may be inferior. Transition temperature (T
g) is too high, and the heat setting property of the obtained catheter tends to be impaired. When the hydrogenation rate of the carbon-carbon bond is less than 70%, the weather resistance and the heat resistance may be poor, and the catheter may be deteriorated during use. Further, the compatibility with the polypropylene resin may be poor, and the transparency of the catheter may be impaired. The polymerization form of isoprene and butadiene is not particularly limited, and may be any form such as random, block, or tapered. Further, the number average molecular weight of the isoprene / butadiene polymer block (hereinafter, sometimes referred to as polymer block C) is not particularly limited, but is preferably 10.0 or less.
It is preferably in the range of 00 to 200,000.

Examples of the hydrogenated block copolymer having a butadiene polymer block include vinyl bonds (1,2 bonds).
When the content is 45% or more and 70% of carbon-carbon double bonds
% Or more is preferably hydrogenated. If the vinyl bond content is less than 45%, the transparency of the catheter may not be sufficient. If the hydrogenation rate of the carbon-carbon double bond is less than 70%, the weather resistance and heat resistance tend to be poor, and the catheter may be deteriorated during use. In addition, the compatibility with the polypropylene resin tends to be poor, and the transparency of the catheter may be impaired. Hereinafter, a butadiene polymer block may be referred to as a polymer block D, and a block copolymer hydrogenated product comprising the polymer blocks B, C, or D may be collectively referred to as a hydrogenated block copolymer (b).

The bonding mode of each polymer block in the hydrogenated block copolymer (b) is not particularly limited, and may be linear, branched, or any combination thereof. A specific example of the molecular structure of the hydrogenated block copolymer is as follows.
(BA) _n , (AB) _n , A (CA) _n , (AC) _n ,
A (DA) _n , (AD) _n (where A represents a polymer block A, B, C, and D represent a polymer block B, a polymer block C, and a polymer block D, respectively, and n is 1 or more. , Etc.). As the hydrogenated block copolymer (b), a star obtained by using divinylbenzene, a tin compound, a silane compound, or the like as a coupling agent (for example, [(AB) mX], where m is an integer of 2 or more) , X
Represents a residue of a coupling agent).

As the hydrogenated block copolymer (b), those having the above-mentioned various molecular structures may be used alone, and for example, a mixture of a triblock type and a diblock type may be used. Two or more compounds having different molecular structures such as those described above may be used in combination. The number average molecular weight of the hydrogenated block copolymer (b) is 30,000 to 300,0.
It is preferably in the range of 00.

The content of the polymer comprising a vinyl aromatic compound in the hydrogenated block copolymer (b) is preferably in the range of 10 to 40% by weight in any of the polymers. If the content of the hydrogenated block copolymer (b) is less than 10% by weight, the mechanical strength of the hydrogenated block copolymer (b) may be insufficient. Further, when the content of the hydrogenated block copolymer (b) exceeds 40% by weight, the melt viscosity of the hydrogenated block copolymer (b) becomes extremely high, and is uniform with the polypropylene resin (a). The mixing tends to be difficult, so that there may be restrictions on the molding process.

As a method for producing the hydrogenated block copolymer (b), a conventionally known production method can be used. For example, the block copolymers obtained by the following methods (a) to (c) can be used. Can be mentioned.
(A) A method in which a vinyl aromatic compound is polymerized using an alkyl lithium compound as an initiator, and then a conjugated diene compound and a vinyl aromatic compound are sequentially polymerized. (B) A method of polymerizing a vinyl aromatic compound and subsequently a conjugated diene compound, and coupling the obtained block copolymer with a coupling agent. (C) A method of polymerizing a conjugated diene compound using a dilithium compound as an initiator and then sequentially polymerizing a vinyl aromatic compound.

In the above method, as the alkyllithium compound, a compound having an alkyl group having 1 to 10 carbon atoms is used. Among them, methyllithium, ethyllithium, pentyllithium, n-butyllithium and s-butyllithium are used.
Butyllithium and t-butyllithium are preferred. Examples of the coupling agent include halogen compounds such as dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and tin tetrachloride; ester compounds such as phenyl benzoate and ethyl acetate; divinylbenzene and various silane compounds. Can be Further, examples of the dilithium compound include naphthalenedilithium and dilithiohexylbenzene. The amount of the initiator or the coupling agent used is appropriately determined depending on the desired molecular weight of the block copolymer.
The initiator is used in an amount of 0.01 to 0.2 parts by weight, and the coupling agent is used in an amount of 0.04 to 0.8 parts by weight based on parts by weight.

The content of the vinyl bond in the hydrogenated block copolymer (b) can be controlled by using a Lewis base as a cocatalyst during the polymerization. Examples of such Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N, N, N ', N'-tetramethylethylenediamine (hereinafter referred to as Is abbreviated as TMEDA), N-
Examples include amine compounds such as methylmorpholine. The amount of the Lewis base used is within the range of 0.1 to 1000 mol per mol of lithium atom in the polymerization initiator.

In the polymerization, an organic compound which is inert to the polymerization initiator is used as a solvent. As such an organic compound, it is preferable to use an aliphatic hydrocarbon having 6 to 12 carbon atoms such as hexane and heptane, an alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, and an aromatic hydrocarbon such as benzene. The polymerization is usually carried out in a temperature range of 0 to 80 ° C. in any of the above polymerization methods (a) to (c). The reaction time is usually 0.5 to 50 hours.

Next, the block copolymer obtained by the above-mentioned method may be dissolved in a solvent inert to the reaction, for example, by reacting with hydrogen in a molecular state in the presence of a known hydrogenation catalyst. Can be used as the hydrogenated block copolymer (b). As the hydrogenation catalyst, a heterogeneous catalyst in which a metal such as Raney nickel, Pt, Pd, Ru, Rh, and Ni is supported on a carrier such as carbon, alumina, and diatomaceous earth, and a Group VIII metal such as nickel and cobalt Catalyst comprising a combination of an organometallic compound and an organoaluminum compound such as triethylaluminum and triisobutylaluminum or an organolithium compound, a bis (cyclopentadienyl) compound of a transition metal such as titanium, zirconium and hafnium and lithium And a metallocene catalyst comprising a combination of organic metal compounds such as sodium, potassium, aluminum, zinc or magnesium. Hydrogenation is
Usually, the reaction is carried out at a hydrogen pressure in the range of normal pressure to 200 kg / cm ² and a reaction temperature in the range of normal temperature to 250 ° C. The reaction time is usually 0.1 to 100 hours. The hydrogenated block copolymer (b) obtained by hydrogenation can be prepared by (i) coagulating the reaction mixture with methanol or the like and then heating or drying under reduced pressure, or (ii) pouring the reaction solution into boiling water, It is obtained by subjecting to so-called steam stripping for removing the solvent by azeotropic distillation, followed by heating or drying under reduced pressure.

The mixing ratio of the olefin resin (a) and the hydrogenated block copolymer (b) in the present invention is in the range of (a) / (b) = 10/90 to 90/10 by weight. . When the proportion of the olefin-based resin (a) is less than 10% by weight, the mechanical strength of the obtained catheter decreases. On the other hand, when the proportion of the olefin resin (a) exceeds 90% by weight, both the transparency and the heat setting property of the catheter deteriorate. The mixing ratio of the olefin resin (a) and the hydrogenated block copolymer (b) is 20/80 to 8 by weight.
The ratio of 0/20 is preferable in terms of transparency, heat setting property, and heat processing property. More preferably, the ratio is 50/50 to 20/80.

The catheter produced from the resin composition of the present invention is suitable as a respiratory catheter or an intravascular catheter, and as long as its properties are not impaired, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring agent, or the like. Agents, crystal nucleating agents, inorganic fillers such as talc, and various additives such as crosslinked beads. The use amount of these additives is usually in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition. In addition, hydrogenated coumarone-indene resin,
A tackifying resin such as a hydrogenated resin such as a hydrogenated rosin resin, a hydrogenated terpene resin, or an alicyclic hydrogenated petroleum resin, or an aliphatic resin composed of an olefin or diolefin polymer can also be added. The amount of these tackifying resins used is
It is less than 200 parts by weight based on 100 parts by weight of the resin composition. Oil such as petroleum hydrocarbons may be added in a range that does not impair the function of the catheter.

In the catheter of the present invention, for example, hydrogenated polyisoprene, hydrogenated polybutadiene, hydrogenated styrene-butadiene random copolymer, hydrogenated styrene-isoprene can be used as long as the gist of the invention is not impaired. Random copolymer, butyl rubber, polyisobutylene, polybutene, ethylene-propylene rubber, polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-
Other polymers such as acrylic acid copolymers and their ionomers, ethylene-ethyl acrylate copolymer, and atactic polypropylene can be blended. Further, the resin composition used in the present invention can be crosslinked by a usual crosslinking method using a peroxide or the like, if desired.

To manufacture the catheter, the polyolefin resin (a) and the hydrogenated block copolymer (b) are kneaded with a kneader such as a kneader, a Banbury mixer, a roll, or the like to form a resin composition. It is formed into a tube by extrusion using a screw extruder, a twin screw extruder, or the like. The resin composition provides a catheter having excellent transparency and heat setting properties. Above all, the transparency is the haze (Ha) when the sheet is 1 mm thick.
ze) value is 20% or less, which is very excellent. The resin composition is excellent in heat resistance, and the obtained catheter withstands autoclave sterilization at 121 ° C. for 20 minutes.
Therefore, when this sterilization method is adopted, the problem of residual ethylene oxide gas is eliminated.

When the catheter is inserted into the trachea as a respiratory catheter, damage to the pharynx, trachea and vocal cords must be suppressed. For this reason, the tube must have an arcuate shape and be easily inserted into the trachea. The curvature diameter of an adult endotracheal catheter is generally about 25 to 31 cm, but in the case of surgery on the face such as the nose and eyes, the respiratory catheter is bent sharply to the lower jaw when it comes out of the lips. It must not be in the way of the field. Therefore, the catheter is required not only to be able to perform a bow-shaped flexible bending process but also to bend sharply to a bending angle of about 180 °. The bending angle is a supplementary angle formed by the intersection of two tangents at both ends of the bent tube.

In order to bend the tube, the tube is fitted into a grooved mold, heated and cooled without kinking, then put into a grooved mold having an increased degree of curvature, and then heated again to cool. Instead of a repetitive method, a grooved mold, a so-called
A method of putting a tube in a flexible tube, heating and cooling without kinking, gradually increasing the curvature of the flexible tube,
Alternatively, a wire or a narrow metal plate is spirally wound around a tube and bent, and heating and cooling are repeated to gradually increase the bending angle.
Among them, the method of spirally winding a linear material around a tube is excellent in workability, reproducibility, and processing accuracy. Specifically, a wire having a diameter of 0.5 mm to 2.5 mm is spirally wound around a tube, and by repeatedly heating and cooling,
The degree of curvature can be gradually increased. After heat setting, even if you remove the wire wound around the tube,
It retains its habit and does not easily return to its original shape. The heating temperature is 70 to 150 ° C., and the cooling may be performed by cooling to room temperature with water or the like. The above operation is repeated to increase the degree of curvature. FIG. 1 is a perspective view showing an example in which a wire is spirally wound around a tube and bent at a bending angle of 180 °, wherein 1 is a wire, and 2 is a tube.

Further, when a catheter is inserted into a blood vessel as an intravascular catheter, at a branched blood vessel site,
You must advance the catheter to either side using a guidewire. For this purpose, it is preferable to curve the end near the distal end of the catheter in advance. Since a small-diameter or thin-walled tube is generally used for the intravascular catheter, it is preferable to use a mold as shown in FIG. 2 or FIG. 3 is a grooved mold having a bending angle of 90 °,
Reference numeral 4 denotes a grooved mold having a bending angle of 180 °. By using such a mold, the tube end can be processed to have a curvature diameter of 1 cm or more and a bending angle of 30 ° to 180 ° or more. In this case, the temperature of the mold is 90 ° C to 15 ° C.
It is carried out at 0 ° C, preferably at 100 ° C to 135 ° C.

When the tube is inserted into the trachea as a respiratory catheter, damage to the pharynx, trachea, and vocal cords must be suppressed. In addition, when the tube is inserted into the blood vessel as an intravascular catheter and is left in place, damage to the blood vessel must be suppressed. Therefore, it is necessary to chamfer the tip of the tube. As a method for chamfering the tip of the tube, there is known a method in which the tip of the tube is cut and the cut end is immersed in an organic solvent to bevel the cut surface, or a method in which the tube is heated with hot air or an incandescent lamp to be chamfered. However, in the method using an organic solvent, since the tube is soluble in the organic solvent, chamfering can be performed, but the tube itself becomes thin and cloudy, and the transparency is impaired. In addition, since the inner diameter is small, the solvent may enter the tube lumen and block it due to capillary action. In the heating of hot air or incandescent lamps, it takes 10 minutes or more to reach a temperature at which chamfering can be performed, that is, a temperature at which melting starts, and workability is poor.

According to the method for manufacturing a catheter of the present invention,
The tip of the catheter is preferably cut at an angle of 45 °,
It is chamfered by being pressed against the hole provided in the mold at 100 to 135 ° C. According to this method, workability, reproducibility, and processing accuracy are excellent. The shape of the hole of the mold includes a hemispherical shape and a conical shape, and preferably, the shape of the cross section of the hole is parabolic. If the temperature of the mold is too high, the phenomenon of fusion of the tube to the mold occurs. If the temperature is too low, it takes a long time to press the tube, which is not practical. Therefore, it depends on the thickness of the catheter. The pressing time is preferably about 30 seconds from the viewpoint of workability.

FIGS. 4 and 5 are schematic diagrams of a concave aluminum mold coated with fluorine. With such a mold, the outer and inner surfaces of the tube can be chamfered simultaneously. 5 is a fluorine-coated aluminum mold for chamfering at an angle of 45 °, and 6 is a chamfering groove for an angle of 45 °. 6 and 7 are schematic diagrams illustrating another example of a fluorine-coated concave aluminum mold, which is used to chamfer only the outer surface of the tube. Reference numeral 7 denotes a fluorine-coated aluminum mold for chamfering the tip of the tube, and reference numeral 8 denotes a bowl-shaped hole for chamfering the tip of the tube. As described above, a bent tube can be obtained, a balloon is bonded to the tube, a branch tube is provided, and a pilot cuff and a connector are attached to obtain a catheter. It is preferable that the tube and the balloon are made of the same material from the viewpoint of adhesiveness.

[0033]

The present invention will be described below in detail with reference to examples. The styrene content, the number average molecular weight, the vinyl bond content and the hydrogenation rate of the polymer in the examples, and the mechanical strength, thermal processability, flexibility, and transparency of the molded product obtained from the resin composition And the heat resistance were determined by the following methods.

Styrene content: Calculated from the weight of each monomer component used in the polymerization. Number average molecular weight: The number average molecular weight ( _Mn ) in terms of polystyrene was determined by GPC measurement. Vinyl bond content: The block copolymer before hydrogenation was dissolved in deuterated chloroform (CDCL3) to give ¹ H-NM.
The R spectrum was measured, and the vinyl bond content was calculated from the size of the peak corresponding to the 1,2-bond or 3,4-bond. Hydrogenation rate: The iodine value of the block copolymer before and after hydrogenation was measured and calculated from the measured value. Mechanical strength of molded product: A sheet having a thickness of 1 mm was prepared, a dumbbell-shaped test piece specified in JIS-3 was punched out of the sheet, and a tensile test was performed in accordance with JIS-K6301. , Breaking strength (Kg / cm ² ) was determined and used as an index of mechanical strength. Flexibility of molded product: 1mm thick sheet is made and AST
The hardness was measured in accordance with MD-2240 and used as an index of flexibility. Transparency of molded product: A sheet with a thickness of 1 mm was prepared and JIS
-Haze menu based on the method specified in K7105
The haze value was measured with a tar and used as an index of transparency. Heat resistance of molded product: A sheet having a thickness of 1 mm was prepared, and the obtained sheet was left in the air at 100 ° C. for 5 hours, and the presence or absence of coloring was visually observed to obtain an index of heat resistance. .

Reference Examples 1-4 (Preparation of hydrogenated block copolymer) In a pressure-resistant container replaced with dry nitrogen, cyclohexane was used as a solvent, and s-butyllithium was used as a polymerization initiator. After polymerizing styrene, TMEDA was added as a Lewis base, and then isoprene and styrene were sequentially polymerized to obtain a styrene-isoprene-styrene type block copolymer. The obtained block copolymer was converted into cyclohexane using Pd / C as a catalyst.
Hydrogenation was performed in a hydrogen atmosphere of 0 kg / cm ² to obtain a hydrogenated block copolymer (hereinafter, the hydrogenated block copolymers obtained in Reference Examples 1 to 4 were each hydrogenated block copolymer 1). ~ 4). Table 1 shows the styrene content, number average molecular weight, vinyl bond content, and hydrogenation rate of the obtained hydrogenated block copolymers 1 to 4.

Reference Examples 5 to 8 (Production of hydrogenated block copolymer) In the same manner as in Reference Examples 1 to 4, s
Styrene, using butyl lithium and TMEDA,
A mixture of isoprene and butadiene [isoprene / butadiene = 60/40 (weight ratio)] and styrene were sequentially polymerized to obtain a styrene- (isoprene / butadiene) -styrene type block copolymer. The obtained block copolymer was hydrogenated in the same manner as in Reference Examples 1 to 4 to obtain a hydrogenated block copolymer (hereinafter, Reference Examples 5 to 5).
The hydrogenated block copolymers obtained in 8 are abbreviated as hydrogenated block copolymers 5 to 8, respectively). Table 1 shows the styrene content, number average molecular weight, vinyl bond content, and hydrogenation ratio of the obtained hydrogenated block copolymers 5 to 8.

Reference Examples 9 to 12 (Production of hydrogenated block copolymer) In the same manner as in Reference Examples 1 to 4, s
Styrene, using butyl lithium and TMEDA,
Butadiene and styrene were sequentially polymerized to obtain a styrene-butadiene-styrene type block copolymer. By hydrogenating the obtained block copolymer in the same manner as in Reference Examples 1 to 4, hydrogenated block copolymers 9 to 12 were obtained.
(Hereinafter, the hydrogenated block copolymers obtained in Reference Examples 9 to 12 are abbreviated as hydrogenated block copolymers 9 to 12, respectively). Table 1 shows the styrene content, number average molecular weight, vinyl bond content, and hydrogenation ratio of the obtained hydrogenated block copolymers 9 to 12.

[0038]

[Table 1]

Examples 1 to 12 and Comparative Example 1 A commercially available polypropylene [
Reference Examples 1-1 using MA-3 manufactured by Mitsubishi Chemical Corporation
The weight ratio of the hydrogenated block copolymers 1 to 12 obtained in 2 to hydrogenated block copolymer / polypropylene resin = 3
It was blended at a ratio of 0/70 and kneaded at 210 ° C. with a kneader to obtain a resin composition. The resin composition was press-formed at 210 ° C. into a sheet having a thickness of 1 mm, and the mechanical strength, flexibility, transparency and heat resistance were measured. Table 2 shows the results. In addition, a sheet having a thickness of 1 mm was prepared in the same manner as described above using the above polypropylene resin alone, and various physical properties were measured (Comparative Example 1). The results are shown in Table 2.

[0040]

[Table 2]

Example 13 The resin composition of Reference Example 1 and polypropylene (F-239, manufactured by Grand Polymer Co., Ltd.) were blended at a ratio of 70/30 (% by weight), and the inner diameter was 7 mm × 220 ° C. using a single screw extruder.
A tube having an outer diameter of 10.2 mm was obtained. The tube was cut to a length of 150 mm, and a wire having a diameter of 1 mm was spirally wound around a wire having a diameter of 1 mm as a "basting" to gradually heat set the tube without kinking.
It was bent in a bow shape. Note that the "curvature diameter" in the present invention is a value obtained by doubling the distance from the center of the fan-shaped bending angle to the outer periphery of the arc tube when the tube is formed into an arc shape, that is, the outer radius.

This was heat-treated at 120 ° C. for 20 minutes in a thermostat, then immersed in water at room temperature and cooled for 3 minutes. Further, heating and cooling operations were repeated stepwise until the tube had a curvature diameter of 5 cm and a U-shape (bending angle of 180 °), and was heat-set until the tube finally changed from a bow shape to a U-shape. The heating temperature was in the range of 70 to 150 ° C., and the heating time was in the range of 10 to 180 minutes. Immediately after heating, it was immersed in water at room temperature and cooled. This operation was repeated three times, and it was possible to form a U-shape having a bending angle of 180 ° without kinking to a desired curvature diameter of 5 cm. Table 3
FIG. 1 shows temperature conditions, heating time, and the state of the tube after heat setting. FIG. 1 is a diagram when a wire is spirally wound around the tube.

[0043]

[Table 3]

Example 14 The resin composition of Reference Example 5 and polypropylene (F-239 manufactured by Grand Polymer Co., Ltd.) were blended at a ratio of 70/30 (% by weight), and the inner diameter was 7 mm × 220 ° C. using a single screw extruder.
A tube having an outer diameter of 10.2 mm was obtained. The tube was cut obliquely at an angle of 45 °, and the cut end was pressed against a fluorine-coated concave aluminum mold at 126 ° C for 30 seconds as shown in FIGS. 4 and 5 to bevel the tip of the tube.
Curved. There was a large difference in the curved surface formation depending on the temperature of the mold and the pressing time. That is, when the temperature is 100 to 13
When the temperature is within the range of 5 ° C., processing can be performed efficiently in a short time. Table 3 shows the curved surface state of the tip of the tube depending on the difference between the temperature of the mold and the pressing time. As is clear from Tables 2, 3, and 4, the resin composition used for the catheter is excellent in transparency, flexibility, heat resistance, heat workability, and has sufficient mechanical strength.

[0045]

[Table 4]

Example 15 The resin composition of Reference Example 9 and polypropylene (F-239 manufactured by Grand Polymer Co., Ltd.) were mixed at a ratio of 70/30 (% by weight), and the inner diameter was 7.0 mm at 220 ° C. using a single screw extruder.
A tube having an outer diameter of 10.2 mm and a length of 150 mm was prepared. A balloon having the same resin composition and a thickness of 100 μm was bonded to the tip. In addition, a tail tube that injects and adjusts anesthetic gas such as air or laughing gas into the balloon and a pilot cuff that monitors the pressure in the balloon with the touch of the hand are attached and attached, and the other end of the tube is attached to a ventilator. And a connector for connecting an anesthesia machine, produce an endotracheal catheter, and sterilize it in an autoclave (121
For 20 minutes). Intubate this catheter into the trachea of the patient in need of artificial ventilation, inject air into the balloon,
Adjusted to moderate pressure (approximately 25 cm H ₂ O). Even when the ventilator was connected to the endotracheal catheter and the catheter was indwelled for two consecutive days, no damage to the pharyngeal mucosa or tracheal mucosa due to contact between the catheter body and the balloon attached to the catheter was observed.

Example 16 The resin composition of Reference Example 1 and polypropylene (F-239 manufactured by Grand Polymer Co., Ltd.) were blended at a ratio of 35/65 (% by weight), and the inner diameter was 0.7 m at 220 ° C. using a single screw extruder.
A tube of mx 1.15 mm outer diameter was obtained. The aluminum mold that had been subjected to the curved surface processing according to the diameter of the tube and the fluorine coating as shown in FIGS. 6 and 7 was heated on a heat block, and was thermoformed while the tip of the tube was pressed against the mold.

Using the mold shown in FIGS. 2 and 3, the mold was heated to 130 ° C. The tip of this tube was pressed into this groove, heat-treated for 10 minutes, then immersed in water at room temperature and cooled for 1 minute. Processing temperature is in the range of 100-150 ° C,
The heating temperature was in the range of 8 to 10 minutes. After heating, it was immersed in room temperature water and cooled. The tip of this tube could be heat set. This heating / cooling operation was sufficient to perform the bending process only once, and no kink or crushing of the tube was observed. Table 5 shows temperature conditions and heating times.

[0049]

[Table 5]

Example 17 The resin composition of Reference Example 1 and polypropylene (F-239 manufactured by Grand Polymer Co., Ltd.) were blended at a ratio of 35/65 (% by weight), and the inner diameter was 0.7 m at 220 ° C. using a single screw extruder.
A tube of mx 1.15 mm outer diameter was obtained. 2 and 3
As shown in the figure, width 1.2 mm, depth 5 mm, curvature diameter 2
A U-shaped groove of cm was dug and the mold was heated to 130 ° C.
This tube was fitted along this groove, heat-treated for 10 minutes, immersed in water at room temperature, and cooled for 1 minute. The processing temperature is in the range of 100 to 150 ° C, and the heating temperature is 8 to 1
Processed within 2 minutes. Immediately after heating, it was immersed in water at room temperature and cooled. The ends near the tip of this tube are L-shaped and U-shaped with a curvature diameter of 2 cm (bending angles 90 ° and 18 °).
0 °). In addition, this heating / cooling operation was sufficient to perform the bending process only once, and no kinking or crushing of the tube was observed. Table 6 shows temperature conditions and heating times.

[0051]

[Table 6]

[0052]

According to the present invention, it is possible to provide a catheter molded from a resin composition having excellent flexibility, transparency, heat processability and flexibility. The catheter of the present invention,
It has excellent heat workability and can be heat-set at a desired angle without kinking, resulting in a radius of curvature of 1 cm.
With the above, the bending angle can be bent to 30 ° to 180 °. Further, according to the present invention, the tip of the catheter can be easily chamfered and curved, and the catheter of the present invention is useful as a respiratory catheter or an intravascular catheter.

[Brief description of the drawings]

FIG. 1 is a perspective view in which a wire is spirally wound around a tube and bent at a bending angle of 180 °.

FIG. 2 is a perspective view of an aluminum mold in which a U-shaped groove having a bending angle of 90 ° is dug.

FIG. 3 is a perspective view of an aluminum mold in which a U-shaped groove having a bending angle of 180 ° is dug.

FIG. 4 is a perspective view of a fluorine-coated aluminum mold for chamfering and bending a tip of a tube having a cutting angle of 45 °.

FIG. 5 is a cross-sectional view of a fluorine-coated aluminum mold for chamfering a tip of a tube having a cutting angle of 45 ° to be curved.

FIG. 6 is a perspective view of a fluorine-coated aluminum mold for chamfering and bending the tip of the tube.

FIG. 7 is a cross-sectional view of a fluorine-coated aluminum mold for chamfering the tip of the tube into a curved surface.

[Explanation of symbols]

Reference Signs List 1 wire 2 tube 3 grooved mold with bending angle of 90 ° 4 grooved mold with bending angle of 180 ° 5 fluorine-coated aluminum mold for chamfering at 45 ° angle 6 groove for chamfering at 45 ° angle 7 tube Fluorine-coated aluminum mold for chamfering the tip 8 Arm-shaped hole for chamfering the tip of the tube

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihide Nakajima 1621 Sazu, Kurashiki-shi, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Masayasu Ogushi 41 41 Miyukigaoka, Tsukuba-shi, Ibaraki Kuraray Co., Ltd. (72) Inventor Satoshi Fukuda 41 Miyukigaoka, Tsukuba, Ibaraki Pref. Kuraray Co., Ltd. (72) Inventor Toshiyuki Zento 41 Miyukigaoka, Tsukuba, Ibaraki Pref. Kuraray Co., Ltd. F-term (reference) CA021 CA022 CA031 CA052 CA121 CA122 CC02 CC05 DA03 DC12 EA02 EA03 EA04

Claims (16)

[Claims] 1. A resin composition comprising an olefin resin, a hydrogenated block copolymer comprising a polymer block comprising one or more vinyl aromatic compounds and a polymer block comprising one or more conjugated diene compounds. A method for producing a catheter, comprising: extruding the resin composition; and repeating heating and cooling. 2. A hydrogenated block copolymer comprising a polymer block comprising a conjugated diene compound, comprising a hydrogenated block copolymer having an isoprene polymer block and a block copolymer hydrogenated having an isoprene / butadiene polymer block. The method for producing a catheter according to claim 1, wherein the catheter is at least one block copolymer hydrogenated selected from a combined hydrogenated product and a block copolymer hydrogenated having a butadiene polymer block. 3. The hydrogenated block copolymer having an isoprene polymer block has a content of 1,2 bonds and 3,4 bonds of 10 to 75% and a carbon-carbon double bond of 70%.
The method for producing a catheter according to claim 1 or 2, wherein at least% is a hydrogenated block copolymer hydrogenated product. 4. A polymer comprising a hydrogenated block copolymer having an isoprene / butadiene polymer block, which is a mixture of isoprene and butadiene in a weight ratio of 5/95 to 95/5, A block copolymer hydrogenated product in which the content of 1,2 and 3,4 bonds is 20 to 85% and 70% or more of carbon-carbon double bonds are hydrogenated. A method for producing a catheter according to any one of the above. 5. The hydrogenated block copolymer having a butadiene polymer block has a 1,2-bond content of 45%.
The method according to any one of claims 1 to 4, wherein the block copolymer is a hydrogenated block copolymer in which 70% or more of the carbon-carbon double bond is hydrogenated. 6. The content of the olefin resin is from 10 to 9.
0% by weight, the content of a block copolymer hydrogenated product comprising a polymer block comprising one or more vinyl aromatic compounds and a polymer block comprising one or more conjugated diene compounds is 90 to 10% by weight. A method for producing a catheter according to any one of claims 1 to 5. 7. The method for producing a catheter according to claim 1, wherein the olefin resin is a polypropylene resin. 8. The method for producing a catheter according to claim 1, wherein the vinyl aromatic compound is styrene. 9. The method according to claim 1, wherein the content of the vinyl aromatic polymer block is 10 to 40% by weight. 10. The method of manufacturing a catheter according to claim 1, wherein the linear object is spirally wound around the tube, heating and cooling are repeated, and the bending angle is gradually increased. 11. The method for producing a catheter according to claim 1, wherein heating and cooling are repeated to bend the end portion to a bending angle of 30 ° to 180 ° with a radius of curvature of 1 cm or more. 12. The method according to claim 1, wherein the distal end of the catheter is
A method for manufacturing a catheter which is brought into pressure contact with a mold heated to about 135 ° C. to be chamfered and curved. 13. A resin composition comprising a hydrogenated block copolymer comprising an olefin resin, a polymer block comprising one or more vinyl aromatic compounds and a polymer block comprising one or more conjugated diene compounds. A catheter obtained by extruding and then repeatedly heating and cooling. 14. The catheter according to claim 13, which is obtained by spirally winding a linear object around a tube, repeating heating and cooling, and gradually increasing the bending angle. 15. The catheter according to claim 13, wherein the end is bent at a bending angle of 30 ° to 180 ° with a radius of curvature of 1 cm or more. 16. The catheter according to claim 13, wherein the distal end is pressure-contacted to a mold heated to 100 to 135 ° C. to be chamfered and curved.