JP2002272834A - Medical molded body - Google Patents

Abstract

[PROBLEMS] To provide mechanical strength, heat resistance, abrasion resistance, recoverability, flexibility, radiation resistance, chemical resistance, pump suitability, non-adsorbent property of a drug, heat sterilization resistance in an autoclave, and the like. An object of the present invention is to provide a medical molded article and a medical device having excellent biocompatibility. SOLUTION: The molded article for medical use is molded from a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or a thermoplastic resin composition containing 5% by weight or more of (A). , Medical tools.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cross-copolymerized
Lefin-aromatic vinyl compound-diene copolymer (A)
Or a suitable amount molded from the resin composition containing (A).
Mechanical properties, pump suitability, abrasion resistance, chemical resistance, non-chemical absorption
The present invention relates to a medical molded article and a medical device having adhesive properties.

More specifically, the present invention relates to an olefin-aromatic vinyl having an aromatic vinyl compound content of 1 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. An olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound, wherein the content of the aromatic vinyl compound in the compound-diene copolymer is at least 5 mol% different from that of the copolymer.
A novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or (A) characterized in that the diene copolymer is cross-copolymerized and has, for example, properties of a thermoplastic elastomer. ) Is formed from a thermoplastic resin composition containing 5% by weight or more, and has mechanical strength, heat resistance, abrasion resistance, recovery, flexibility, flexibility, radiation resistance,
Antifogging properties, chemical resistance, (elastic recovery, stress relaxation properties, drawdown resistance during molding), pump suitability, drug non-adsorption,
The present invention relates to a medical molded article and a medical device such as an autoclave, which have a well-balanced performance excellent in heat sterilization resistance and biocompatibility and do not generate a chlorine compound as a gas during incineration.

[0003]

2. Description of the Related Art Tubes generally used for instillation,
Medical devices such as catheters, blood circuits, etc., bags, containers such as blood, infusions and dialysis, and medical devices comprising them are not only flexible and flexible, but also have radiation resistance, biocompatibility, especially blood Excellent compatibility is required. Furthermore, strength that can withstand the operation is also required. In particular, it is required that the tube has moderate elongation elasticity and adhesiveness, and has a so-called stiffness. Conventionally, it is often manufactured using soft PVC which is a material having these properties.
Further, in recent years, disposable medical molded articles or medical devices formed therefrom have been promoted, and incineration after use has increased in order to prevent biohazard. A medical molded article using soft PVC generates a chlorine compound as a gas during incineration, so that environmental load has been considered, and an alternative to a soft PVC medical molded article is being studied. A chlorine-free film, a medical molded article made of a linear low-density ethylene-α-olefin-based copolymer or a medical device made of the same as a tube is known. Or a medical device consisting of it has not yet emerged.

Japanese Patent Application Laid-Open No. 4-159344 discloses a resin composition which is excellent in flexibility and provides a molded product suitable for medical use. A resin composition comprising a hydrogenated product of an isoprene block copolymer has been proposed. This resin composition provides a molded article having excellent flexibility, and has the characteristic that even if the molded article is incinerated, no toxic gas is generated. However, since such a resin composition is expensive in terms of the cost of the hydrogenated polymer used, a molded article or a medical device comprising the same is disadvantageous in cost as compared with soft PVC and is not suitable for disposable applications. .

[0005] In addition, it has been reported that a composition comprising a non-flexible PVC resin, specifically, a composition composed of a styrene-based elastomer, polypropylene, and the like and a composition of a citrate ester has a function of suppressing hemolysis of red blood cells. Tokiohei 3-20
No. 2298, and a thermoplastic polyester composition disclosed in Japanese Patent Application Laid-Open No. 6-319785. Compared with the hemolytic inhibitory action of the agent, it is not sufficient and is not practical.

[0006] Among the catheters, a balloon catheter in which the balloon is inflated in a blood vessel and then deflated and left for several days has a problem that when the surface is loosened, a blood clot is easily generated due to stagnation of blood flow. . The gastrointestinal catheter is repeatedly pulled by the peristaltic motion of the gastrointestinal tract. Therefore, in the case of such an application, it is required to have excellent strain recovery. Conventional catheters using thermoplastic polyurethane have excellent mechanical properties, but have the drawback of poor strain recovery.

Further, WO98 / 12252, JP-A-2000-325465, EP1062957
The A1 publication describes a styrene-ethylene random copolymer having specific characteristics and a tube, a catheter, and the like obtained by molding the composition, but it has strength, abrasion resistance, heat resistance to a sterilization process, and the like. There were unsatisfactory points.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide, in addition to the strength, flexibility and flexibility required for medical applications,
Excellent biocompatibility including radiation resistance, stress at high strain, pump durability, chemical resistance, stress relaxation properties, and blood compatibility, excellent heat resistance in sterilization process, and substantially contains chlorine It is an object of the present invention to provide a molded article for medical use which does not generate chlorine compound gas during incineration and a medical device comprising the same.

[0009]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A)
Alternatively, the present inventors have found that a medical molded article molded from a thermoplastic resin composition containing (A) and a medical device comprising the same are suitable, and have completed the present invention.

That is, according to the present invention, the aromatic vinyl compound content is 1 mol% or more and 96 mol% or less, and the diene content is 0.00
An olefin-aromatic vinyl compound-diene copolymer having an olefin content of from 01 mol% to 3 mol%, with the balance being olefin,
The content of the aromatic vinyl compound is 5 mol% as compared with the copolymer.
The novel olefin-aromatic vinyl compound copolymer and / or olefin-aromatic vinyl compound-diene copolymer is characterized by being cross-copolymerized. It is molded from a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or a thermoplastic resin composition containing 5% by weight or more of (A), and has mechanical strength, heat resistance, wear resistance, and recovery. , Flexibility, flexibility, radiation resistance, anti-fog properties, chemical resistance, elastic recovery, stress relaxation properties, draw down resistance during molding, pump suitability, non-adsorbent properties, autoclave and other heat sterilization resistance Further, the present invention provides a medical molded article and a medical device comprising the same, which have a well-balanced performance excellent in biocompatibility and do not generate a chlorine compound as a gas during incineration.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or a medical composition molded from a resin composition containing 5% by weight or more of (A). A molded article and a medical device comprising the same. Hereinafter, (A) will be described in detail.

[Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A)] The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) of the present invention (hereinafter referred to as "cross copolymer") Is an olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 1 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. And a cross copolymer obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content differing by 5 mol% or more. It is a polymerized olefin-aromatic vinyl compound-diene copolymer.

As used herein, the term “cross-copolymer” means that a main-chain olefin-aromatic vinyl compound-diene copolymer and a vinyl compound polymer are linked via a diene unit at one or more points as shown in FIG. Bond with cross strand (cross-link)
It is a copolymer mainly having the structure shown below. Such a cross structure can be rephrased as a star structure. In addition, classification by the American Chemical Society POLY subcommittee
graded star copolymer
(Polymer prints, 1998,
March). Hereinafter, the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer cross-linked to the main chain olefin-aromatic vinyl compound-diene copolymer is referred to as a cross chain. . On the other hand, as shown in FIG. 2, a graft copolymer known to those skilled in the art is a copolymer mainly having a polymer chain branched from one or more points of a main chain. A structure in which the polymer main chain and other polymer chains cross-link (cross-link) (also referred to as a star structure) generally has a higher polymer microstructure than a grafted structure when used as a composition or compatibilizer. It is believed that excellent strength of the structural interface is obtained, giving high mechanical properties.

The cross-copolymer constituting the present invention has an aromatic vinyl compound content of 1 mol% to 96 mol%.
Hereinafter, the olefin-aromatic vinyl compound-diene copolymer having a diene content of 0.0001 mol% or more and 3 mol% or less and the balance being an olefin is added to an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing a compound-diene copolymer, wherein the cross-linked aromatic vinyl compound content of the cross-chain is cross-copolymerized. A cross-copolymerized olefin-aromatic vinyl compound, which differs from the aromatic vinyl compound content of the main chain olefin-aromatic vinyl compound-diene copolymer by at least 5 mol% before the polymerization.
It is a diene copolymer. More preferably, the cross copolymer constituting the olefin resin composition of the present invention has an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less,
An olefin-aromatic vinyl compound-diene copolymer having a diene content of 0.0001 mol% or more and 3 mol% or less, with the balance being an olefin, and an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-
Cross-copolymerized olefin characterized by being cross-copolymerized with a diene copolymer-aromatic vinyl compound-
A cross-copolymer, which is a diene copolymer, wherein the content of the aromatic vinyl compound is at least 5 mol% different from that of the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, which is a functionalized olefin-aromatic vinyl compound-diene copolymer.

The cross copolymer used in the present invention is:
Not only is it a concept showing the cross copolymer itself,
Cross copolymer, and the first polymerization step shown below, non-cross-linked olefin obtained in the second polymerization step-
The term includes a composition containing an aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer in an arbitrary ratio. The composition containing such a cross copolymer can be obtained by the following production method.

An example of the method for producing the cross-copolymer used in the present invention will be described, but is not limited to the following production method. The cross-copolymer production method is preferably uniform and can be produced with efficiency and economy suitable for industrialization. That is, as a first polymerization step, an olefin monomer, an aromatic vinyl compound monomer and a diene monomer are copolymerized to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then as a second polymerization step, the copolymerization is performed. Polymers and olefin and aromatic vinyl compound monomers,
If necessary, this is a method for producing a cross-copolymer by cross-copolymerization using a diene monomer. First polymerization step,
A coordination polymerization catalyst is preferably used in the second polymerization step, and a single-site catalyst is particularly preferable.

The aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step and the olefin-aromatic vinyl compound copolymer polymerized in the second polymerization step (first polymerization step) When the polymerization solution obtained in the step is used as it is in the second polymerization step, a small amount of the residual diene is copolymerized in the polymer obtained here). It is necessary to be. Preferably at least 10 mol%,
Most preferably, they differ by at least 15 mol%. Preferably, the olefin obtained in the first polymerization step
The aromatic vinyl compound content of the aromatic vinyl compound-diene copolymer and the aromatic vinyl compound content of the finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer are at least 5 mol%, preferably at least 5 mol%. Is different by 10 mol% or more.

The olefins used in the first polymerization step include ethylene, α-olefins having 3 to 20 carbon atoms,
That is, propylene, 1-butene, 1-hexene, 4-
Examples include methyl-1-pentene, 1-octene and cyclic olefins, ie, cyclopentene and norbornene. Preferably, ethylene, ethylene and propylene, 1
Α- such as butene, 1-hexene or 1-octene
A mixture with an olefin, an α-olefin such as propylene is used, and more preferably, ethylene, ethylene and α
A mixture of olefins is used, particularly preferably ethylene.

Styrene is preferably used as the aromatic vinyl compound used in the first polymerization step, but other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butylstyrene, α-methylstyrene, vinyl Naphthalene, p-methylstyrene, vinyl naphthalene,
Vinyl anthracene or the like can be used, and a mixture thereof may be used.

As the diene used in the first polymerization step, a diene capable of coordination polymerization is preferably used. For example, butadiene, isoprene, chloroprene and the like described in JP-A-6-136060, and paradivinylbenzene and metadivinylbenzene described in JP-A-11-124420 are exemplified. Preferably 1,4-hexadiene, 1,5-
Hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1cyclohexene, 3-vinyl-1cyclohexene, 2-vinyl-
1-cyclohexene, 1-vinyl-1-cyclohexene, paradivinylbenzene, metadivinylbenzene or a mixture thereof is used. Further, a diene in which a plurality of double bonds (vinyl groups) are bonded via a hydrocarbon group having 6 to 30 carbon atoms containing one or more aromatic vinyl ring structures can be used. Preferably, dienes in which one of the double bonds (vinyl group) is used for coordination polymerization and the remaining double bond in the polymerized state is coordinatively polymerizable, most preferably para, meta divinyl Benzene and mixtures thereof are preferably used.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step has an aromatic vinyl compound content of 1 mol% to 96 mol% and a diene content of 0.0001 mol% to 3 mol%. The balance is preferably an olefin, preferably an aromatic vinyl compound content of 1 mol% to 50 mol%, a diene content of 0.001 mol% to less than 0.5 mol%, and a balance of olefin. When the content of the aromatic vinyl compound is 1 mol% or less, chemical resistance,
The scratch resistance (scratch resistance) becomes insufficient, and if it is 96 mol% or more, the mechanical properties, chemical resistance, and the like become insufficient.

When the first polymerization step is carried out at a diene concentration higher than the required amount, a large amount of the crosslinked structure of the polymer is formed during the polymerization to cause gelation or the like. It is not preferable because the processability and physical properties of the polymer deteriorate. For example, if the first polymerization step is performed at a diene concentration higher than the required amount, the residual diene concentration in the polymerization liquid will increase. Also, the obtained cross-copolymer similarly deteriorates processability and physical properties.
Conversely, if the first polymerization step is carried out at a diene concentration less than the required amount, the crossing density is small and the crossing effect is not sufficient. When the gel content of the cross-copolymer is 10% by weight or more, moldability such as fluidity is remarkably reduced, which is disadvantageous when the molded article is recycled. From these, the amount of the diene used in the first polymerization step is preferably 1/100 or less with respect to the amount of the aromatic vinyl compound used in a molar ratio.
/ 50,000 or more, more preferably 1/400 or less
It is 20,000 or more.

The single-site coordination polymerization catalyst preferably used in the first polymerization step includes a polymerization catalyst comprising a transition metal compound and a co-catalyst, soluble Zieglar-N
Atta catalysts, transition metal compound catalysts activated with methylaluminoxane, boron compounds, and the like (so-called metallocene catalysts, half-metallocene catalysts, CGCT catalysts, and the like) are exemplified. Specifically, polymerization catalysts described in the following documents and patents can be used. For example, in the case of metallocene catalysts, US Pat.
No. 88, JP-A-6-49132, Polym
er Preprints, Japan, 42, 229
2 (1993), Macromol. Chem. ,
Rapid Commun. , 17, 745 (199
6), JP-A-9-309925, EP08724
92A2, JP-A-6-184179. In half metallocene catalysts, Makromol. Chem.
191, 387 (1990). For CGCT catalysts, JP-A-3-1630088, JP-A-7-53618, and EP-A-416815. Soluble Zieg
For the lar-Natta catalyst, JP-A-3-250007
No., Stud. Surf. Sci. Catal. ,
517 (1990). An olefin-aromatic vinyl compound-diene copolymer having a uniform composition in which the diene is uniformly contained in the polymer is preferably used.To obtain a copolymer having such a uniform composition, Zieglar
It is difficult with a -Natta catalyst, and a single-site coordination polymerization catalyst is preferably used. A single-site coordination polymerization catalyst is a polymerization catalyst composed of a transition metal compound and a co-catalyst, and a transition metal compound catalyst activated by methylaluminoxane, boron compound, or the like (a so-called metallocene catalyst, half metallocene catalyst, CGCT catalyst, etc.). ).

The most preferably used single-site coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a promoter. When a polymerization catalyst composed of a transition metal compound represented by the following chemical formula (1) and a cocatalyst is used, it is possible to copolymerize a diene, particularly divinylbenzene, with a polymer with high efficiency. It is possible to reduce the amount of diene used in the first polymerization step and the amount of unreacted diene remaining in the polymerization solution.

Further, when a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a co-catalyst is used, an olefin-aromatic vinyl compound having a high activity and a uniform composition suitable for industrialization- It is possible to produce diene copolymers. An olefin-aromatic vinyl compound-diene copolymer having isotactic stereoregularity and a head-tail styrene chain structure in a composition having an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less. Can be.

Embedded image In the formula, A and B are each independently a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. . Y has a bond to A and B, and further contains a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms (this group has 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atom. (Which may be included) as a substituent.
The substituents may be different or the same. Also, Y
May have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group. X is each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms,
An aryl group having 10 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or hydrogen, or a hydrogen atom having 1 to 22 carbon atoms. An amide group having a hydrocarbon substituent. n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium. Particularly preferably, at least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group, and the transition metal compound of the above general formula (1) and a cocatalyst. And a polymerization catalyst.

As the cocatalyst used in the first polymerization step, known cocatalysts and alkylaluminum compounds conventionally used in combination with a transition metal compound can be used. As such a cocatalyst, methylaluminoxane (Or as methylalumoxane or MAO)
Alternatively, a boron compound is suitably used. Examples of cocatalysts and alkylaluminum compounds used include EP
-0872492A2, JP-A-11-13080
No. 8, JP-A-9-309925, WO00 /
Co-catalysts and alkylaluminum compounds described in JP-A-20426, EP0985689A2, and JP-A-6-184179.

In producing the olefin-aromatic vinyl compound-diene copolymer, each monomer, metal complex (transition metal compound) and co-catalyst exemplified above are brought into contact with each other. Can be used. As a method of the above first polymerization step, a method of polymerizing in a liquid monomer without using a solvent,
Or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene,
There is a method in which a saturated aliphatic or aromatic hydrocarbon such as chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform or the like or a halogenated hydrocarbon is used alone or in a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization. If necessary, known methods such as batch polymerization, continuous polymerization, and multistage polymerization can be used.

It is also possible to use a single linear or loop, or a plurality of connected pipes. In this case, the pipe-shaped polymerization can includes various known mixers such as a dynamic or static mixer and a static mixer that also serves as heat removal, a cooler equipped with a heat removal thin tube, and the like. It may have various known coolers. Moreover, you may have a batch type pre-polymerization can. Further, a method such as gas phase polymerization can be used.
The polymerization temperature is suitably from -78 ° C to 200 ° C. -7
Polymerization temperatures below 8 ° C. are industrially disadvantageous, 200 ° C.
If it exceeds, the metal complex is decomposed, which is not suitable.
More preferably, it is industrially preferably 0 ° C to 160 ° C, particularly preferably 30 ° C to 160 ° C. The pressure during the polymerization is generally from 0.1 to 1000 atm, preferably from 1 to 100 atm, particularly preferably 1 to 100 atm.
-30 atm.

When an organic aluminum compound is used as a cocatalyst, an aluminum atom /
The complex metal atom ratio is 0.1 to 100,000, preferably 1
Used at a ratio of 0 to 10,000. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a co-catalyst, a boron atom / complex metal atom ratio of 0.01 to 1 is used.
It is used at a ratio of 00, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

In the first polymerization step of the present invention, the olefin partial pressure can be changed continuously or stepwise within a range of less than 150% or more than 50% of the olefin partial pressure at the start of the polymerization. However, the olefin partial pressure in the first polymerization step is preferably kept constant during the polymerization. The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is preferably an ethylene-styrene-diene copolymer, or an ethylene-α-olefin-styrene-diene copolymer, or an ethylene-cyclic copolymer. An olefin-styrene-diene copolymer, particularly preferably an ethylene-styrene-divinylbenzene copolymer is used. Further, the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step may have a cross structure or a cross-linked structure with the diene monomer unit contained, but the gel content is 10% by weight of the whole. , Preferably less than 1% by weight.

Hereinafter, typical and suitable ethylene-styrene-divinylbenzene copolymers used in the present invention will be described. The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has a head-tail styrene unit chain structure attributed to a peak observed at 40 to 45 ppm by 13C-NMR measurement based on TMS. And preferably 42.3-43.1 ppm, 43.7-44.5 p
pm, 40.4-41.0 ppm, 43.0-43.6
It preferably has a chain structure of styrene units assigned by the peak observed in ppm.

Further, ethylene-styrene-divinylbenzene copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene and producing polyethylene by homopolymerization of ethylene. Coalescing is preferred. Therefore, the obtained ethylene-styrene-divinylbenzene copolymer can have both an ethylene chain structure, a head-tail styrene chain structure, and a structure in which an ethylene unit and a styrene unit are bonded in the main chain.

The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step, which is preferably used, has a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (1) contained in the structure. Is a copolymer having a stereoregularity of isotactic dyad fraction (or meso dyad fraction) Pm of more than 0.5, preferably more than 0.75, particularly preferably more than 0.95. The isotactic dyad fraction Pm of the alternating copolymer structure of ethylene and styrene has a peak area Ar derived from an r-structure of a methylene carbon peak appearing at around 25 ppm by 13C-NMR measurement based on TMS, and an m-structure. From the area Am of the peak derived,
It can be obtained by the following equation (1). Pm = Am / (Ar + Am) General formula (1) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. The m structure is a meso diad structure,
The r structure represents a racemic diad structure.

The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has an alternating structure having a ratio of an alternating structure of styrene and ethylene represented by the following general formula (2) contained in the copolymer structure. The index λ is smaller than 70, larger than 0.01, preferably smaller than 30,
Preferably, the copolymer is greater than 0.1. λ = A3 / A2 × 100 General formula (2) Here, A3 is obtained by 13 C-NMR measurement and has three types of peaks a, b, and 3 derived from an ethylene-styrene alternating structure represented by the following chemical formula (2) This is the sum of the areas of c. A2 is 13C-NMR based on TMS.
Is the sum of the areas of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm.

Embedded image (In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

In particular, a copolymer having a high isotactic stereoregularity in the ethylene-styrene alternating structure and having an alternating structure index λ of less than 70 is preferred as the copolymer of the present invention. -A copolymer having a styrene chain of a tail, and having an isotactic stereoregularity in an ethylene-styrene alternating structure, and having an alternating structure index λ value of less than 70 is particularly preferred as the copolymer of the present invention. . That is, the olefin-aromatic vinyl compound-diene copolymer obtained in the preferred first polymerization step used in the present invention has an ethylene / styrene alternating structure having high stereoregularity, and simultaneously ethylene chains of various lengths,
It has the characteristic of having various structures such as styrene hetero bonds and styrene chains of various lengths. Further, the olefin-aromatic vinyl compound-diene copolymer of the present invention, the polymerization catalyst used and the polymerization conditions, the ratio of the alternating structure depending on the aromatic vinyl compound content in the copolymer, the λ value obtained by the above formula Can be variously changed within a range of more than 0.01 and less than 70.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step suitably used in the present invention, particularly the ethylene-styrene-divinylbenzene copolymer described above, has the above-mentioned chemical formula ( It can be obtained by a polymerization catalyst comprising the transition metal compound represented by 1) and a co-catalyst. As described above, ethylene-styrene as a representative and preferred example obtained in the first polymerization step in producing an olefin-aromatic vinyl compound-diene copolymer
Although the divinylbenzene copolymer has been described, the olefin-aromatic vinyl compound-diene copolymer used in the present invention is not limited to this.

The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is as follows:
It is 10,000 or more, preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less, preferably 500,000 or less. The molecular weight distribution (Mw / Mn) is at most 6, preferably at most 4, most preferably at most 3. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC with standard polystyrene. The same applies to the following description. The weight-average molecular weight of the olefin-aromatic vinyl compound-diene copolymer used in the present invention may be adjusted within a range described above by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature if necessary. Can be adjusted. The olefin obtained in the first polymerization step
The aromatic vinyl compound-diene copolymer may partially have a cross structure or a branched structure via the included diene unit.

Next, the second polymerization step will be described. The second polymerization step here may be composed of a plurality of polymerization steps having different conditions and the like. As the second polymerization step, coordination polymerization using a single-site coordination polymerization catalyst is preferably employed. More preferably, a single-site coordination polymerization catalyst comprising the same transition metal compound represented by the chemical formula (1) and a cocatalyst as in the first polymerization step is employed. The single-site coordination polymerization catalyst composed of the transition metal compound represented by the chemical formula (1) and the co-catalyst forms a residual coordination polymerizable double bond of a diene unit copolymerized in a polymer main chain, particularly, divinylbenzene. Because it can be copolymerized with high efficiency,
It is also preferred as a catalyst for the second polymerization step. The copolymer obtained in the second polymerization step preferably has the same structure as the copolymer in the first polymerization step, but the composition is such that the content of the aromatic vinyl compound is that of the copolymer in the first polymerization step. It is necessary that the difference be at least 5 mol%.

In the second polymerization step, for example, a method similar to the polymerization method used in the above-mentioned first polymerization step is used. In this case, olefins and aromatic vinyl compounds used in the first polymerization step, and diene monomers remaining as needed or remaining in the polymerization solution can be used. The second polymerization step is preferably performed following the first polymerization step using the polymerization liquid obtained in the first polymerization step. However, the copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, and a monomer such as an olefin is newly added. A two-polymerization step may be performed.

The olefin-aromatic vinyl compound copolymer or olefin-aromatic vinyl compound which is polymerized in the second polymerization step compared to the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step The aromatic vinyl compound content of the diene copolymer (when the polymerization solution obtained in the first polymerization step is used as it is in the second polymerization step, a small amount of residual diene is copolymerized in the obtained polymer) is at least It is necessary that they differ by 5 mol%. Preferably it differs by at least 10 mol%, most preferably by at least 15 mol%. The aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are at least 5%.
Preferably, they differ by at least mol%.

If the aromatic vinyl content of the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step do not differ by at least 5 mol%, the polymer obtained in the first polymerization step as a cross copolymer While only the average physical properties of the polymer obtained in the second polymerization step are obtained, when the content of the aromatic vinyl compound is different by 5 mol% or more, the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step are obtained. The characteristics of both polymers appear. The features include, for example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like. These features are combined, and various properties can be simultaneously provided. Further, the aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are preferably different from each other by 5 mol% or more. When the aromatic vinyl compound content of the polymer obtained in the polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer differ from each other by 5 mol% or more, the polymer obtained in the first polymerization step and the second polymerization step The characteristics of both of the polymers obtained in the above appear.

The polymer obtained in the second polymerization step may have a branched structure via a diene unit contained. A specific manufacturing method satisfying the above is described below. That is, as a first polymerization step, an aromatic vinyl compound monomer, an olefin monomer and a diene monomer are copolymerized using a coordination polymerization catalyst to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then As the second polymerization step under different polymerization conditions, this olefin-aromatic vinyl compound-diene copolymer and at least olefin, aromatic vinyl compound, in the presence of diene if necessary,
This is at least a two-stage polymerization method in which polymerization is performed using a coordination polymerization catalyst. Further, the production method preferably satisfies at least one or more of the following conditions. 1) The olefin partial pressure of the polymerization solution in the second polymerization step is 1 to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step.
50% or more or 50% or less. 2) The concentration of the aromatic vinyl compound in the polymerization liquid immediately before the start of the polymerization in the second polymerization step is 30% or less, or 20% or less, of the concentration of the aromatic vinyl compound immediately before the start of the polymerization in the first polymerization step.
0% or more. 3) Use different single-site coordination polymerization catalysts in the first polymerization step and the second polymerization step. 4) In the first polymerization step and the second polymerization step, the type of olefin used for the polymerization is different. Here, the first polymerization step and the second polymerization step are distinguished when the operation for changing these conditions is started.

The change satisfying the above conditions is performed as rapidly as possible and completed, preferably within 50%, more preferably within 30%, even more preferably within 10% of the polymerization time of the second polymerization step. It is preferable to complete. Further, the polymerization temperature in the first polymerization step and the polymerization temperature in the second polymerization step are preferably the same. If different, a temperature difference within about 100 ° C. is appropriate. As a method of changing the monomer composition ratio in the polymerization liquid, for example, the olefin partial pressure of the polymerization liquid in the second polymerization step is set to 150% or more, preferably 200% or more, and most preferably 300% to the first polymerization step.
There is a way to change it. As an example, when ethylene is used as the olefin, the ethylene pressure is 0.2 MPa.
When the first polymerization step is performed in the second polymerization step, the first polymerization step is performed at 0.3 MPa or more, preferably 0.4 MPa or more, and most preferably 0.6 MPa or more. Further, the olefin partial pressure of the polymerization solution in the second polymerization step may be changed to 50% or less, preferably 20% or less with respect to the first polymerization step. For example, when the first polymerization step is performed at an ethylene pressure of 1.0 MPa, the second polymerization step is performed at 0.5 MPa or less, preferably 0.2 MPa or less. If the olefin partial pressure of the second polymerization step satisfies the above conditions,
It may be constant during the polymerization, or may be changed stepwise or continuously.

Further, as an example of a method for changing the monomer composition ratio in the polymerization solution, the concentration of the aromatic vinyl compound in the polymerization solution immediately before the start of the polymerization in the second polymerization step is shorter than that immediately before the start of the polymerization in the first polymerization step. 30% or less, preferably 20% or less, or 200% or more, preferably 500%
The above-mentioned changing method is also applicable. For example, when styrene is used as the aromatic vinyl compound, when the first polymerization step is started at a styrene concentration of 1 mol / L in the polymerization liquid, 0.3 mol / L or less, preferably 0.1 mol / L or less in the second polymerization step. It is carried out at 2 mol / L or less, or 2 mol / L or more, preferably 5 mol / L or more. Furthermore, you may apply combining the said olefin partial pressure and the change of an aromatic vinyl compound density | concentration.

The copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, an olefin and an aromatic vinyl compound monomer are added, and the copolymer is added in the presence of a single-site coordination polymerization catalyst. When performing the two polymerization step,
A single site polymerization catalyst different from the first polymerization step can be used. In the first polymerization step and the second polymerization step, by changing the type of olefin used for the polymerization, the aromatic vinyl compound content of the copolymer polymerized in the first polymerization step and the second polymerization step is as described above. It is also possible to change it.

The second polymerization step is carried out subsequent to the first polymerization step using the polymerization solution obtained in the first polymerization step, and without adding a new aromatic vinyl compound monomer. When the monomer remaining in the liquid is used in the second polymerization step, the conversion of the aromatic vinyl compound monomer species through all the polymerization steps is preferably at least 50% by weight, particularly preferably at least 60% by weight. is there. The higher the conversion of the aromatic vinyl compound monomer through the second polymerization step or all the polymerization steps, the higher the probability that the polymerizable double bond of the diene unit of the copolymer main chain is cross-copolymerized.

In the production of the cross copolymer, preferably, among the conditions described in paragraph 0042, 1)
Alternatively, a manufacturing method that satisfies 2) is adopted, and among the above conditions, a manufacturing method that satisfies 1) is more preferably adopted. In the production method that satisfies 1), a method is more preferably employed in which the olefin partial pressure of the polymerization solution in the second polymerization step is changed to 300% or more with respect to the first polymerization step. When the olefin partial pressure in the first polymerization step is not constant, that is, when the olefin partial pressure fluctuates within the above range, the polymerization in the second polymerization step is preferably performed with respect to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step. A method is employed in which the olefin partial pressure of the polymerization liquid immediately before the start is maintained at 300% or more.

The proportion of the copolymer obtained in the first polymerization step is at least 10% by weight or more, preferably at least 30% by weight of the finally obtained cross copolymer. The amount of the polymer (including the cross chain weight) obtained in the second polymerization step is at least 10% of the finally obtained cross copolymer.
% By weight, preferably 30% by weight or more. If either of them is 10% by weight or less or 90% by weight or more, the characteristics of the polymer having a small amount of components are not sufficiently exhibited. For example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like are mentioned.
If the content is more than 10% by weight, these features cannot be provided together, and as a result, various properties as exemplified above cannot be simultaneously provided. Here, the aromatic vinyl content of the finally obtained cross copolymer is preferably from 1 mol% to 96 mol%, and the diene content is from 0.0001 mol% to 3 mol%.
It is preferably at most mol%.

The first polymerization step and the second polymerization step can be carried out in different reactors. These steps can also be performed using a single reactor. Cross-copolymerization of olefins, aromatic vinyl compounds, and dienes using a coordination polymerization catalyst in a single reactor while continuously changing the olefin or aromatic vinyl compound concentration You can also.

The physical properties of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer as a typical example of the cross-copolymer of the present invention will be described below. The cross copolymer (A) used in the present invention has, for example, thermoplastic elastomer-like properties. Further, it is characterized in that the composition of the main chain and the cross chain (styrene content in the case of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer) is largely different. Either the main chain or the cross chain can have a composition having a low styrene content (that is, a crystal structure derived from an ethylene chain). Further, the cross-copolymer of the present invention has different styrene contents corresponding to the styrene contents of the main chain and the cross-chain, respectively.
A styrene copolymer (which may contain a small amount of divinylbenzene) can be contained in any ratio. This is because the cross copolymer functions as these compatibilizers, and thus can have various characteristics.

When ethylene is used as the olefin, the cross copolymer can have a crystal structure derived from an ethylene chain, and thus has good heat resistance. Further, the ethylene-styrene copolymer having a low styrene content can have characteristics such as a low glass transition temperature, a low embrittlement temperature (−50 ° C. or lower), and high mechanical properties (rupture strength, tensile elastic modulus). . In addition, since it can have a composition having a relatively high styrene content in either the main chain or the cross chain, it can have characteristics of an ethylene-styrene copolymer having a relatively high styrene content shown below. . That is, a relatively low tensile modulus, surface hardness, flexibility, and a tan δ component near room temperature in the viscoelastic spectrum (0.05 to 2.0 at 0 ° C. or 25 ° C., preferably 0.1 to 0.80).
In addition, it can have scratch resistance, PVC-like feel, coloring, and printability. That is, it is superior in heat resistance, compatibilization, scratch resistance, abrasion resistance, chemical resistance and the like as compared with the conventional ethylene-styrene copolymer.

The cross copolymer used in the present invention is D
The melting point is preferably from 65 ° C to 140 ° C by SC,
More preferably, at least one is observed at 80 ° C. or more and 130 ° C. or less, and its melting point is 10 J / g or more,
J / g or less, preferably 20 J / g or more and 120 J / g or less. The cross copolymer used in the present invention preferably has a crystal structure based on an ethylene chain structure. This crystal structure can be confirmed by a known method, for example, an X-ray diffraction method. further,
The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 mol% or more and 5 mol% or more.
0 mol% or less, the aromatic vinyl compound content,
Heat of crystal fusion measured by DSC is 10 J / g or more and 150 J
/ G or less preferably satisfies the following relationship. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; The heat of crystal fusion measured by DSC is 10 J / g or more and 1
Melting point (° C.) not more than 50 J / g St; Aromatic vinyl compound content (mol%) Known so-called pseudo-random copolymers, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher melting point than the olefin-aromatic vinyl compound random copolymer.

When the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 mol% to 20 mol%, the aromatic vinyl compound content and the Vicat softening point are as follows: It is preferable to satisfy the relationship. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 1
40 Tvicat; Vicat softening point (° C.) St; Aromatic vinyl compound content (mol%) This relationship is known from JP-A-3-1630088 and JP-A-7-53618 when the same aromatic vinyl compound content is used. A so-called pseudo-random copolymer, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher Vicat softening point than the olefin-aromatic vinyl compound random copolymer.

The cross copolymer of the present invention has a higher heat resistance and a lower heat resistance than a conventional random copolymer having no cross structure.
Excellent strength, scratch resistance, abrasion resistance, stress relaxation properties, and moldability such as elongational viscosity and melt tension. In the medical molded article of the present invention, the cross copolymer is 5
It is molded from a thermoplastic resin composition containing at least 20% by weight, preferably at least 20% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight. If the amount is less than 5% by weight, characteristics inherent to the cross copolymer, such as heat resistance, mechanical properties such as strength, and chemical resistance, cannot be sufficiently exhibited.

Examples of the olefin polymer which can be blended in the present invention include high-density polyethylene, low-density polyethylene, ethylene-α-olefin copolymer composed of ethylene and α-olefin having 3 to 8 carbon atoms, ethylene-
One or more olefin-based polymers selected from vinyl acetate copolymers and homopolypropylenes can be mentioned. For example, isotactic polypropylene,
Syndiotactic polypropylene, atactic polypropylene, linear low density polyethylene (L-LDP
E), low density polyethylene (LDPE), propylene-
Ethylene copolymer, block of ethylene, propylene and butene, hexene, α-olefin such as octene, random copolymer, polymethylpentene, polybutene-1,
Examples thereof include an ethylene-acrylate copolymer, an ethylene-methacrylate copolymer, an ethylene-vinyl acetate copolymer, and an ionomer resin.

In the present invention, the styrene polymers which can be blended include polystyrene, rubber-reinforced polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-methacrylic acid ester copolymer, and styrene. At least one selected from a butadiene random copolymer, a styrene-butadiene block copolymer and a hydrogenated product thereof, a styrene-isoprene block copolymer and a hydrogenated product thereof. For example, polystyrene (atactic, isotactic, syndiotactic), styrene-methacrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-
Butadiene block copolymer (SBS) and its hydrogenated product (SEBS), styrene-butadiene rubber (SBS)
BR) and its hydrogenated product, butadiene rubber (B
R), styrene-isoprene block copolymer (SI
S) and its hydrogenated product (SEPS), styrene-
Butadiene-methyl methacrylate copolymer (MBS)
And the like.

The blend amount of the olefin polymer and the styrene polymer is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 50% by weight.
It is as follows. If it exceeds 95% by weight, characteristics inherent to the cross copolymer, for example, mechanical properties such as heat resistance, strength, and chemical resistance cannot be sufficiently exhibited.

In addition to olefin-based polymers and styrene-based polymers, various resins such as polyphenylene ether,
Various random, block, and homopolymers such as polymethyl methacrylate and 1,2-polybutadiene can be added. The addition amount is not particularly limited as long as the strength and heat resistance of the present invention are not impaired, but is preferably 50% by weight or less, more preferably 30% by weight or less.

The molded article for medical use of the present invention may contain a plasticizer for the purpose of adjusting the flexibility, the temperature dependence of physical properties, and the like. Known plasticizers are used, for example, phthalates, pyromellitic esters, trimellitic esters, trimesic esters,
Benzoic acid ester, adipic acid ester, azelaic acid ester, sebacic acid ester, phosphate compound, epoxy compound, polyester compound, aromatic, aliphatic and other hydrocarbon oils, such as paraffin oil, naphthenic oil, etc. One type can be added. Preferred plasticizers include low molecular weight organic ester compounds, and hydrocarbon oils,
Of these, the following phthalate plasticizers are particularly preferred.

Specific examples of preferred plasticizers in consideration of the leaching property and the effect on the human body are dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-n-octyl phthalate, and phthalic acid. Di-n-decyl, di-n-lauryl phthalate, undecyl phthalate, tetra-n-octyl pyromellitic acid, tri-n-octyl pyromellitic acid, triisooctyl trimellitate, tri-2-trimellitic acid Ethylhexyl, trimesic acid tri (2,2-dimethylpentyl) ester, trimesic acid tri (2-ethylhexyl) ester, benzoic acid diester, di-2-ethylhexyl adipate, diisodecyl adipate, dicapryl adipate, di-2 azelate -Ethylhexyl, di-2-ethylhexyl sebacate, dibu sebacate Le, tricresyl phosphate, triphenyl phosphate, phosphoric acid diphenyl cresyl, tributyl phosphate, epoxy hexahydrophthalic acid dioctyl,
Epoxidized soybean oil, methyl epoxystearate, adipic acid-based polyester, sebacic acid-based polyester and the like can be mentioned.

The molecular weight of the plasticizer is not particularly limited, but the low molecular weight organic ester compound is preferably 25.
A range of 0 to 800, more preferably about 300 to 600 is suitable. If the molecular weight is too low, there is a problem of volatility,
If the molecular weight is too high, the molecules are less likely to move through the composition, so that the molecules are less likely to leach into the erythrocyte-containing liquid, particularly in blood bag applications, and as a result, the protective action of the erythrocytes (haemolysis suppressing action) may be reduced. The compounding amount of the plasticizer is preferably 0.1 to 0.1 in the resin composition containing (A) or (A).
The content is from 01 to 80% by weight, more preferably from 0.1 to 50% by weight, particularly preferably from 0.3 to 30% by weight. If the amount is too small, the softening may be insufficient. If the amount is too large, the plasticizer may bleed out. In addition, it is preferable to add a plasticizer to the blood bag in order to suppress the hemolysis.

In the medical molded article of the present invention, it is necessary to prevent the moisture in the air from aggregating on the surface of the tube, catheter, bag, container, etc., thereby clouding the medical molded article and making it difficult to confirm the contents. For the purpose of prevention, an antifogging agent may be added as necessary. Alternatively, a method of applying the composition to the surface of a medical molded article may be used. As the antifogging agent, those generally used can be used as they are, and examples thereof include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, fatty acid amines, and fatty acid amides. Among these, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyalkylene ethers, and fatty acid amines are particularly preferable. The compounding amount of the antifogging agent is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight in the resin composition containing (A) or (A). If the amount is too small, the anti-fogging effect may be insufficient. If the amount is too large, the physical properties may be reduced.

In the present invention, an anti-blocking agent can be added. Although there is no particular limitation on the applicable antiblocking agent, examples thereof include amide compounds such as ethylenebisamide and stearic acid amide, carboxylic acids such as stearic acid, and carboxylic acid salts such as zinc stearate. The amount of the antiblocking agent is not particularly limited, but is preferably 1% by weight or less. When the amount exceeds 1% by weight, the strength, heat resistance, etc. of the molded article for medical use may be reduced.

The (A) or the thermoplastic resin composition containing (A) of the present invention is selected from petroleum resins having a glass transition temperature of 20 ° C. or higher, terpene resins, cumarone-indene resins, rosin resins and hydrogenated products thereof. It is possible to include at least one type of resin. The above-mentioned resin is not particularly limited, and examples thereof include petroleum resins, terpene resins, cumarone-indene resins, rosin-based resins, and hydrogenated products thereof having various compositions and molecular weights. When the glass transition point is less than 20 ° C., it is suitable as a molded article for medical use,
For example, elastic recovery at room temperature, suitability for a packaging machine, and the like may be insufficient. The amount of the resin having a glass transition point of 20 ° C. or higher is preferably 50% by weight or less, more preferably 30% by weight or less. If it exceeds 50% by weight, properties such as strength and elastic recovery at room temperature are deteriorated.

The molded article for medical use of the present invention may further comprise, if necessary, a stabilizer, an antioxidant, a light resistance improver, an ultraviolet absorber, a plasticizer, a softener, a lubricant, a processing aid, in addition to the above-mentioned components. ,
A coloring agent, an antistatic agent, a crystal nucleating agent and the like can be added. These can be used alone or in combination of two or more.

The cross copolymer (A) used in the present invention
Is a material having excellent transparency when the homogeneity of the microstructure is high, that is, when at least one of the main chain and the cross chain takes a dispersion structure as a dispersed phase having an average of preferably 3 μm or less, or has a microphase separation structure. Can be obtained.
When transparency is required, the ratio contained in the resin composition is preferably the cross copolymer (A) of the present invention.
Is 80% by weight or more, more preferably 95% by weight or more, particularly preferably 98% by weight or more.

Further, the resin, elastomer, rubber, and the like having a refractive index value close to that of the transparent cross copolymer selected as described above and having excellent transparency and the like.
There is a method of imparting transparency by blending with an additive or the like.
In this case, the difference between the two refractive index values is preferably 0.2 or less,
More preferably 0.05 or less, particularly preferably 0.02
It is as follows. Furthermore, in this case, if the difference between the values of the compatibility parameters is within a certain range, the transparency can be further improved. Specifically, 5 (cal / cm3) ^1/2 or less is preferable, and 3 (cal / cm3) ^1/2 or less is more preferable.
1 (cal / cm3) ^1/2 or less is particularly preferable. The refractive index of the resin, elastomer, rubber, additive, etc. to be blended,
The value of the compatibility parameter can be determined, for example, by WILLY INTERSCIENCE.
This is described in, for example, the third edition of Polymer Handbook published by K.K. Furthermore, when the resin, elastomer, rubber, additives, etc. are dispersed in fine particles, preferably 0.5 μm or less, more preferably 0.2 μm or less, particularly preferably 0.05 μm or less, excellent transparency is obtained. Material. In particular, the film of the present invention made by the extrusion method is
When the above conditions are satisfied, the film has excellent transparency with a total light transmittance of usually 80% or more, preferably about 88% or more. The total light transmittance (or total light transmittance) is, for example, JIS K-
It can be measured by the method described in 7361-1, K-7105 and the like.

The molded article for medical use of the present invention has a dynamic viscoelastic spectrum measured at a frequency of 1 Hz of 0 ° C. to 30 ° C.
It is preferable that the maximum value and the minimum value of the loss tangent tan δ in are respectively 0.5 or more and 0.05 or more. Further, the difference between the maximum value and the minimum value is preferably 2.0 or less,
1.0 or less is more preferable. If the conditions are not satisfied, the stress relaxation characteristics at 0 ° C. to 30 ° C. may be insufficient, and the recoverability as a medical molded article may be insufficient. Further, if only one or two of the three conditions are satisfied, the temperature dependence of the tan δ characteristic becomes too strong,
It may not be possible to satisfy the above characteristics uniformly at any temperature in the range of 0 to 30 ° C.

The method for producing the medical molded article of the present invention can be appropriately selected depending on the shape of the medical molded article. For example, known molding methods such as extrusion molding, injection molding, compression molding, blow molding, rotational molding, calender molding, thermoforming, cast molding and the like can be mentioned. It is also possible to combine a plurality of molding methods. For the production of multilayer sheets,
A laminating method is also applicable. In order to prevent blocking between sheets, the inner and outer surfaces of the container may be roughened, that is, embossed, or an anti-blocking agent, a slip agent or the like may be added. In any of the molding methods, the principle is that the material is heated, melted or softened and deformed by an external force to obtain a desired shape. Affects the physical properties of When the medical molded article of the present invention is in the form of a film or a sheet, a normal extrusion film molding method such as an inflation method or a T-die method, or a press molding method or an injection molding method can be employed. In the case of a tube shape, for example, extrusion molding can be used. In addition, roll molding, injection molding, rotational molding and the like can be applied according to the shape and application. When the medical molded article of the present invention is, for example, a film, a sheet, or a bag, the thickness is not particularly limited, but is generally 3 μm to 1 mm, preferably 10 μm to 0.5 mm.

The cross-copolymer contained in the molded article for medical use and the medical device of the present invention may be used, if necessary, by crosslinking by a usual crosslinking method using a peroxide, an electron beam, radiation or the like. Is also possible.

In the molded article for medical use of the present invention, for example, a sheet base material for a bag such as a blood bag, an infusion bag, a dialysis bag, or a pharmaceutical aqueous solution bag is a single layer or a laminate including a layer containing a cross copolymer. And In the case of a laminate, this means a case where the sheet substrate includes at least one layer made of a resin composition containing a cross copolymer and at least one layer made of another resin component. In the case of a laminate, a layer made of another resin component is used for the purpose of adjusting and improving the mechanical properties, moldability, heat sealability, blocking resistance, heat resistance, and the like of the bag. Also,
Similarly, in the case of a tube and a catheter, a multilayer structure can be formed of different kinds or similar kinds of resin, metal, and the like. As a resin component forming a layer composed of another resin component as a resin component forming a layer of the laminate, polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polypropylene, poly-4-methyl Penten-1,
Examples thereof include polyamide, polyether amide (a block copolymer of polyether and polyamide), polyurethane, thermoplastic polyester, and 1,2-polybutadiene.

The medical molded article of the present invention can be subjected to surface treatment such as corona, ozone, plasma, etc., antifogging agent application, lubricant application, printing, etc., as required. The medical molded article of the present invention can be uniaxially or biaxially stretched as required. The molded body for medical use of the present invention may be joined to the same material or a material such as a thermoplastic resin, if necessary, by a method such as fusing by heat, ultrasonic waves, high frequency or the like, or bonding by a solvent or the like. Can be.

The thermoplastic resin composition for forming the molded article for medical use of the present invention can be mixed by a known method. That is, there is no particular limitation on the method of mixing the resin composition containing the cross copolymer (A), the thermoplastic resin, the plasticizer, and, if necessary, other additives, and a known method can be used. . For example, dry blending can be performed using a Henschel mixer, a ribbon blender, a super mixer, a tumbler, or the like.
The melt-mixing may be performed using a co-kneader, a roll, or the like. If necessary, the reaction can be performed in an atmosphere of an inert gas such as nitrogen.

The molded article for medical use is used in various forms such as a film, a sheet, a catheter, a tube, a container and the like. The required mechanical strength differs for each application. In the medical molded article of the present invention, a medical molded article having a wide range of physical properties can be provided by changing the content of the aromatic vinyl compound in the cross-copolymer and the amount of the plasticizer added. For example, a feeding catheter is required to have low hardness and flexibility for insertion into a body. In addition, since the tube is repeatedly pulled by peristalsis, if the material has a large permanent elongation, the surface will loosen, causing blood flow stagnation,
Clots are more likely to occur. Therefore, the copolymer preferably has an elongation at break of 200% or more and a permanent elongation of 60% or less. When confirmation of the contents is required, transparency is required, and examples thereof include the copolymers of Examples 1, 4, and 5.

Conventionally, medical molded articles made of soft PVC are generally sterilized using ethylene oxide gas (EOG). However, there is a concern that the residual EOG may adversely affect the patient's health. It is preferable to eliminate the influence of the above, and it is conceivable to switch to another sterilization method. The molded article for medical use and the medical device of the present invention are preferable in that a gamma ray sterilization method can be applied and this method that does not leave residue can be applied. Under the γ-ray sterilization conditions usually used in the medical field, the medical molded article and medical device of the present invention are less likely to cause a decrease in molecular weight and a remarkable decrease in mechanical properties such as elongation and breaking strength. According to the γ-ray sterilization method, a crosslinking reaction can be performed at the same time as sterilization, and it is also possible to simultaneously modify physical properties such as a physical property such as an elastic modulus.

The molded article for medical use and the medical device of the present invention can be prepared by subjecting autoclave sterilization conditions usually carried out in the medical field to:
For example, under conditions of about 1 hour at 120 ° C. to 130 ° C., deformation due to the generation of melting, wrinkling, and the like is unlikely to occur. For this reason, it has autoclave sterilization suitability. Further, the molded article for medical use of the present invention has good biocompatibility. Especially excellent in blood compatibility. In particular, in the case of an application to be inserted into a blood vessel, the medical molded article of the present invention can impart antithrombotic properties to the surface in contact with the liquid. As a method for imparting antithrombotic properties, a known method can be used. For example, heparin, urokinase, or the like can be immobilized to a reactive functional group of a catheter base by covalent bonding, ionic bonding, adsorption, or the like. .

Next, a medical molded article and a medical device according to the present invention will be described. Medical molded articles such as catheters inserted into the respiratory tract, trachea, gastrointestinal tract, urethra, blood vessels, and other body cavities or tissues do not damage the tissues and allow smooth insertion to the target site. When excellent lubricity is required to avoid the possibility of damaging the mucous membrane or causing irritation due to friction during placement in the tissue, A coating of a lubricating resin may be formed entirely. For example, a coating can be formed by covalently bonding a water-soluble polymer such as a maleic anhydride-based polymer. The molded article for medical use of the present invention, taking advantage of the above characteristics, for example, catheters such as indwelling catheters and balloon catheters, artificial blood vessels, blood circuits, syringes, artificial dialysers, blood component separators, artificial lungs, wounds It is used as a medical molded article such as a covering material, a sanitary material such as a sanitary article, a disposable diaper, and a medical article such as a surgical garment and a hospital disposable sheet. Among them, taking advantage of excellent biocompatibility, medical tubes, catheters, artificial blood vessels, blood circuits, syringes, hemodialyzers, blood component separators, artificial lungs, etc. It is suitably used as a medical molded article to be used. Not all of these medical molded articles need be formed from the resin composition for medical molded articles of the present invention. For example, in the above-mentioned tubes, catheters, blood bags, and the like, a portion that comes into contact with a body fluid is formed of the resin composition for a molded article of the present invention, and a portion that does not come into contact with the body fluid is used for other medical uses such as polyurethane. It may be formed of resin. In addition, the medical molded article of the present invention includes a medical container as one of them, and can be suitably used in applications requiring excellent flexibility and transparency.

More specifically, examples of the medical molded article and medical device of the present invention include the following, but the present invention is not limited thereto. A. Angiographic catheter, cerebrovascular catheter,
Intravascular insertion or indwelling catheters such as thermodilution catheter, IVH catheter, indwelling needle, etc.
Or dilators, stylets, introducers, and guidewires for these catheters. B. Various balloons or balloon catheters. C. Catheters that are inserted or placed in the digestive tract orally or nasally, such as a gastric tube catheter, a feeding catheter, and a tube for tube feeding. D. Oral or nasal catheters such as oxygen catheters, oxygen cannulas, tubes and cuffs for endotracheal tubes, tubes and cuffs for tracheostomy tubes, and intratracheal suction catheters. E. FIG. Catheters to be inserted or placed in various body cavities or tissues such as suction catheters, waste catheters, peritoneal catheters, rectal catheters, urethral catheters, and trocar tubes. F. Endoscope tube inserted into various body cavities.

G. Stents, artificial blood vessels, artificial trachea,
Artificial bronchi, colostomy, etc. H. Various medical instruments such as an artificial lung, an artificial heart, an artificial kidney, a reservoir, a bubble trap, a drip chamber, and the like, and members constituting an extracorporeal circuit such as a circuit tube forming a blood flow path. I. Bags such as a blood bag, an infusion bag, an infusion bag, and a waste liquid bag, or members such as tubes and connectors connected to these bags. J. Test instruments and treatment instruments that require low frictional resistance (lubricity) when placed in the body and sliding, test instruments and treatment instruments that require antithrombotic properties. K. Various air supply tubes and liquid supply tubes. L. contact lens.

[0080]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. The copolymer obtained in each of the following Reference Examples was analyzed by the following means. The 13C-nmr measurement was performed using a device manufactured by JEOL Ltd. α-50.
0, the solvent used was heavy 1,1,2,2-tetrachloroethane, and the measurement was performed based on tetramethylsilane (TMS). Here, the measurement based on TMS is as follows. First, weight 1,1, based on TMS
The shift value of the central peak of the triplet 13C-nmr peak of 2,2-tetrachloroethane was determined. Next, the copolymer was dissolved in heavy 1,1,2,2-tetrachloroethane to obtain 1
3C-nmr was measured, and each peak shift value was
Calculated based on the triplet center peak of 1,2,2-tetrachloroethane. The shift value of the triplet center peak of heavy 1,1,2,2-tetrachloroethane is 73.89 pp.
m. The measurement was carried out using 3 parts of the copolymer against these solvents.
The dissolution was performed by weight / volume%. At the end of the first and second polymerization steps, the amount of divinylbenzene in the polymerization liquid was determined by gas chromatography measurement of the polymerization liquid extracted at the end of the second polymerization step, and the amount of divinylbenzene consumed in the first and second polymerization steps From this value, the divinylbenzene content of the polymer obtained in the first polymerization step and the divinylbenzene content of the finally obtained cross copolymer were obtained.

The determination of the styrene content in the copolymer is as follows.
The peak was derived from a phenyl group proton based on TMS using a 1,1,2,2-tetrachloroethane solvent (6. H-nmr). 5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 3 ppm). The molecular weight was determined using GPC (gel permeation chromatography) in terms of standard polystyrene. The measurement was performed using tetrahydrofuran (THF) as a solvent and HLC-8020 manufactured by Tosoh Corporation as a measuring instrument. The DSC was measured using a DSC200 manufactured by Seiko Denshi Co., Ltd. at a temperature rising rate of 10 ° C./min under a nitrogen stream. For a copolymer insoluble in THF at room temperature, ortho-dichlorobenzene was used as a solvent, and Tosoh HLC-812 was used as a measuring instrument.
The measurement was performed at 145 ° C. using No. 1. The gel content was measured as follows according to ASTM D-2765-84. About 1.0 g of the precisely weighed polymer (molded product having a diameter of about 1 mm and a length of about 3 mm) was wrapped in a 100-mesh stainless steel net bag and weighed accurately. After extracting this in boiling xylene for about 5 hours, the net bag is collected,
Dried in vacuum at 90 ° C for more than 10 hours. After cooling sufficiently, the net bag was precisely weighed, and the amount of polymer gel was calculated by the following equation. [Gel content (%)] = [weight of polymer remaining in mesh bag after test (g)] / [weight of polymer in mesh bag before test (g)] × 100

The physical properties of the resin compositions of the examples were evaluated by the following methods. The molded piece was formed by press molding, and the shape and thickness were changed according to each test as necessary. <Hardness> The hardness of a durometer type A was measured at 23 ° C. according to JIS K7215. <Vicat softening point> Load 1 according to JIS K7206
The Vicat softening point was measured in kgf. However, in the case of the reference example, the Vicat softening point was measured under a load of 200 gf.

The mechanical strength, flexibility, transparency, and biocompatibility of the resin compositions obtained in the examples were measured by the following methods. <Mechanical Strength of Molded Article> A medical tube having an outer diameter of 3.5 mm and an inner diameter of 2.5 mm is formed by a single-screw extruder, and this tube is used and according to the tensile test method of JIS K-7113. Tensile modulus, elongation at break, yield strength at break, strength at break at 100 mm / min, 100%
Modulus and 300% modulus were determined and used as indexes of mechanical strength. <Permanent elongation> 1cm marked using the above tube
Was stretched to 100% (2 cm) between the marked lines, stretched and held for 10 minutes, and then released for a further 10 minutes. The length between the marked lines was measured to measure the residual permanent strain. The permanent elongation was expressed as a ratio (%) of the elongation to the original length. <Flexibility> A molded piece having a thickness of 5 mm is manufactured and subjected to JIS K-
The durometer hardness of types D and A was determined according to the durometer hardness test method of No. 7215, and used as an index of flexibility. <Transparency of molded article> A sheet having a thickness of 1 mm was prepared and JI
Haze was determined by the method specified in SK-7361-1 using a Nippon Denshoku turbidimeter NDH-2000.

<MFR> The MFR was measured in accordance with JIS K-7210, a thermoplastic plastic flow test method. The measurement was performed at a measurement temperature of 230 ° C. and a test load of 10 kgf. <Chemical resistance> In the solvent resistance test, the films and sheets were immersed at room temperature for one week, and then evaluated by visual observation, tactile sensation and weight measurement. ◎: No change Swelling rate 10% or less ：: Swelling rate 10 to 40% △: Slightly gelling, dissolving or solidifying ×: Gelling, dissolving or solidifying

<Heat Sterilization> Using the tube obtained in the above molding, sterilization was carried out for 1 hour at 121 ° C. in an autoclave for heat sterilization (Model SS-320, manufactured by Tommy). Shrinkage (%) (10)
Judging comprehensively such as 0 × length after sterilization / original length), melted state, wrinkle, etc., heat sterilization resistance was evaluated in three stages (good, normal,
X poor). <Pump durability> Tube (outer diameter 3.5
mm, inner diameter 2.5 mm), and a liquid sending test was carried out with a medical metering pump (250 ml / hr for 1 day). Change in flow rate (%) after one day, and change in tube appearance (scratched,
Comparison of crushing, elongation and generation of powder, good ○ (good), △
(Normal), x (degraded), the durability was evaluated.

<Drug Adsorbability> A tube (outer diameter 3.5 mm, inner diameter 2.5 mm) was prepared using an extruder, and a liquid sending test was performed using an aqueous nitroglycerin solution. The change in nitroglycerin concentration at the tube outlet was measured. After 3 hours, the drug non-adsorption property was evaluated by the retention (%) with respect to the initial concentration. <Scratch resistance> The scratch level of sapphire having a load of 500 g and a tip diameter of 0.05 mm-R was evaluated using a press-formed sheet using a scratch tester of Toyo Seiki Co., Ltd. It was comprehensively evaluated according to the depth and width of the scratch, and classified into に (good), Δ (middle), and × (poor). <Taber abrasion test> According to ASTM F-510,
Wear (mg) due to the worn wheel was measured. Load 1kg, number of revolutions 9000.

Reference Example 1 <Synthesis of cross-copolymerized ethylene-styrene-divinylbenzene copolymer (C-1)> rac-dimethylmethylenebis (4,5-benzo-1-indenyl) was used as a catalyst.
It carried out as follows using zirconium dichloride. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Toluene 440
0 mL, 400 mL of styrene, and 0.5 mL of divinylbenzene (purity: 80%, manufactured by Aldrich) were charged, and heated and stirred at an internal temperature of 70 ° C. About 100 L of nitrogen was bubbled through to purge the system and the polymerization solution. Triisobutylaluminum 8.4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-s) is 21 based on Al.
mmol, ethylene was immediately introduced, and the pressure was 0.2
After stabilizing at 5 MPa (1.5 kg / cm 2 G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were added from a catalyst tank installed on an autoclave. About 50 ml of the dissolved toluene solution was added to the autoclave. 70 internal temperature
The polymerization was carried out for 46 minutes while maintaining the pressure at 0.25 MPa at ° C (first polymerization step). The consumption of ethylene at this stage was about 100 L under standard conditions. A part of the polymerization solution was sampled, and a polymer sample (polymer 1-A) in the first polymerization step was obtained by meta-precipitation. Ethylene was rapidly introduced, and the pressure in the system was adjusted to 1.1 MPa over 25 minutes. By increasing the pressure of ethylene, polymerization was promoted, and the internal temperature was temporarily increased from 70 ° C to 80 ° C. Polymerization was performed for 25 minutes while maintaining the pressure at 1.1 MPa (second polymerization step). After completion of the polymerization, the obtained polymer solution was added little by little into a large amount of vigorously stirred methanol solution to recover the polymer. The polymer was air-dried at room temperature for 24 hours, and then dried at 80 ° C. in vacuo until no change in mass was observed. 860 g of a polymer (Polymer 1-C) was obtained. Table 1 shows the polymerization conditions of Reference Example 1 and Table 2 shows the polymerization conditions.
Shows the results of analysis of the obtained cross-copolymerized ethylene-styrene-divinylbenzene copolymer. Further, the polymer produced in the second polymerization step (1-
The calculated value of B) is shown in the table.

Reference Examples 2 to 5 Polymerization and post-treatment were carried out in the same manner as in Reference Example 1 under the conditions shown in Table 1. Table 2 shows the analysis results of the obtained cross-copolymerized ethylene-styrene-divinylbenzene copolymers. The results of calculating the components generated in the second polymerization step from the polymerization conditions and the polymerization results shown in Tables 1 and 2 are also 2-B to
5-B is also shown in Table 2.

[0089]

[Table 1]

[0090]

[Table 2]

Reference Example 6 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. After the atmosphere in the system was replaced with nitrogen, 62 L of dehydrated cyclohexane and 10 L of dehydrated styrene were charged into a polymerization vessel, and heated and stirred at an internal temperature of 60 ° C. 84 mmol of triisobutylaluminum and 84 mol of methylalumoxane (PMAO-s, manufactured by Tosoh Akzo Co., Ltd.) based on Al
mmol was added. Immediately introduced ethylene, pressure 1.
After stabilizing at 0 MPa, the catalyst, rac dimethyl methylene bis (4,5-
84 μmol of benzo-1-indenyl) zirconium dichloride, 2 mmol of triisobutylaluminum
About 100 ml of a toluene solution in which was dissolved was added to the polymerization vessel. The polymerization was carried out for 120 minutes while maintaining the internal temperature at 60 ° C. and the ethylene pressure at 1.0 MPa. After depressurizing ethylene,
The polymerization vessel gas phase was purged several times with nitrogen. Next, the polymerization solution was put into 150 L of 85 ° C. heated water containing a dispersant (Pluronic P-103; manufactured by Asahi Denka Co., Ltd.) with vigorous stirring over 1 hour. After stirring at 97 ° C for 30 minutes,
Hot water containing crumbs was put into the cooling water, and the crumbs were collected. The crumb was air-dried at 50 ° C. to obtain 7 kg of a copolymer (SE1) having a crumb shape with a size of about several mm and having a good shape. The composition ratio of styrene and ethylene is 18 mol% and 8
It was 2 mol%. Table 3 shows the polymerization conditions of Reference Example 4, and Table 4 shows the analysis results of the obtained ethylene-styrene random copolymer.

<Reference Example 7> Polymerization and post-treatment were carried out in the same manner as in Reference Example 4 under the conditions shown in Table 3. Table 3 shows the polymerization conditions of Reference Example 7, and Table 4 shows the analysis results of the obtained styrene-ethylene random copolymer.

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

Examples 1 to 6 and

Comparative Examples 1 to 4 The resin compositions obtained in Reference Examples 1 to 5 were extruded, and tensile properties, flexibility, and workability were evaluated in tubes prepared. The results are shown in Tables 5 and 6. Shown in As comparative examples, soft vinyl chloride (described as PVC), 1,2
-Polybutadiene was used.

[0096]

[Table 5]

[0097]

[Table 6]

When Examples 1 to 6 and Comparative Examples 1 to 4 are compared, the examples have the following features. Compared to PVC, breaking strength, elongation, chemical resistance, tensile recovery, drug non-adsorption,
Also, as compared to 1,2-polybutadiene, the breaking strength,
Excellent in scratch resistance, abrasion resistance, chemical resistance, tensile recovery rate, heat sterilization, and pump durability.

<Γ-ray sterilization test>

Examples 7 to 13 and Comparative Examples 5 to 8
Tubes molded from each resin composition were also used, placed in polyethylene bags and placed in cardboard boxes. Each cardboard box was irradiated with 25 kGray γ-rays, which is a normal sterilization condition. After the irradiation, the respective changes in mechanical strength, flexibility and Mw (the ratio of post-irradiation / initial value (%)) and the degree of coloring were measured.
Table 7 shows the results.

[0100]

[Table 7]

In Examples 7 to 13, the respective values of the breaking strength, elongation and tensile modulus did not decrease after irradiation and no coloring was observed as compared with Comparative Examples 5 to 8.

<Biocompatibility test>

Examples 14 to 16 A catheter having a length of 30 cm, an outer diameter of 2.6 mm and an inner diameter of 1.6 mm was obtained by extruding each of the resin compositions shown in Table 8 and a soft vinyl chloride for a control example into a tube. Produced. Each of the obtained catheters was inserted into a rabbit jugular vein and left for 7 days. At this time, the inside of the catheter was filled with physiological saline, and the end outside the body from the vein was sealed. The catheter was removed from the rabbit jugular vein, washed with saline, immobilized by treating the surface with glutaraldehyde and osmium oxide, and fibrin and platelets on the outer surface of the catheter were observed with the naked eye and an electron microscope. Table 8 shows the results. On the outer surface of the catheter, fibrin and platelets equivalent to or less than those of the soft vinyl chloride of the control example were observed in the tubes made of any of the resin compositions of Examples 14 to 16.

[0103]

[Table 8]

[0104]

The novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) of the present invention and the medical device and the medical device formed from the resin composition containing (A) are excellent. It is suitable for use in the medical field because it has excellent flexibility and moderate elasticity, as well as radiation resistance, drug non-adsorption, pump suitability, biocompatibility and chemical resistance.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a structure mainly contained in a cross-linked copolymer of the present invention.

FIG. 2 is a conceptual diagram showing the structure of a conventional grafted copolymer.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08J 5/00 CER C08L 51/00 4J128 C08K 5/00 A61L 33/00 A C08L 51/00 Z F term (reference) 4C081 AC06 AC08 AC12 AC14 AC15 AC16 BB02 BB03 BB05 BB07 BB08 CA031 CA081 CA121 CC03 DA02 DA03 EA05 4F071 AA12X AA14X AA15X AA19 AA20X AA22X AA71 AA77X AC10 AC15 AE04 AE11 AE22 AF02 BC05 BC02 AF02 AF14 BC05 CF002 EH046 EH086 EH146 EP016 EP026 EW046 FD022 FD026 FD176 FD206 GB01 4J026 AA12 AA17 AA18 AC36 BA02 BA05 BA07 BB04 BB10 DA02 DA08 DA17 DB02 DB09 DB17 DB24 FA08 GA01 GA02 GA08 4J028 AA01AC01BA01B01B01B01B EB11 EB21 EC04 ED01 ED06 ED09 FA02 FA08 GA07 GA19 4J128 AA01 AB01 AC01 AC09 AC27 AD00 BA00A BA01B BB00A BB01B BC00A BC12B BC14B BC15B BC25B EA02 EB02 EB11 EB21 EC04 ED01 ED06 GA07 GA19 FA08

Claims (24)

[Claims] 1. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or (A)
A medical molded article or a medical device comprising the molded article, wherein the molded article is formed from a thermoplastic resin composition containing not less than 10% by weight. (A): An olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, with the balance being olefin. Olefin-aromatic vinyl compound copolymer and / or olefin whose aromatic vinyl compound content is different from the copolymer by 5 mol% or more.
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the aromatic vinyl compound-diene copolymer is cross-copolymerized. 2. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) or (A)
A medical molded article or a medical device comprising the molded article, wherein the molded article is formed from a thermoplastic resin composition containing not less than 10% by weight. (A): An olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, with the balance being olefin. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer. Wherein the content of the aromatic vinyl compound differs from that of the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization by 5 mol% or more. Vinyl compound-diene copolymer. 3. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is copolymerized with an aromatic vinyl compound monomer, an olefin monomer and a diene monomer by using a coordination polymerization catalyst as a first polymerization step. Polymerization is performed to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then, as a second polymerization step having different polymerization conditions therefrom, the olefin-aromatic vinyl compound-diene copolymer and at least an olefin monomer, The molded article for medical use according to claim 1 or 2, wherein the molded article is produced by using at least a two-stage polymerization method in which polymerization is carried out using a coordination polymerization catalyst in the presence of an aromatic group vinyl compound monomer. Medical tools. 4. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A), wherein the polymer produced in the first polymerization step is 10% by weight to 90% by weight and the polymer produced in the second polymerization step is 4. The medical molded article according to claim 3, wherein the amount of the polymer is 90% by weight to 10% by weight. Here, the total of the polymer produced in the first polymerization step and the polymer produced in the second polymerization step is 1
00% by weight. 5. The medical device according to claim 1, wherein the gel content of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is less than 10% by weight. Or a medical device comprising the same. 6. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is produced by a single-site coordination polymerization catalyst comprising a transition metal compound and a co-catalyst. Item 6. A medical molded article according to any one of Items 1 to 5, or a medical device comprising the same. 7. A coordination polymerization catalyst for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) comprises a transition metal compound represented by the following chemical formula (1) and a co-catalyst. The medical molded article according to claim 6, which is a polymerization catalyst to be produced, or a medical device comprising the same. Embedded image In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
It is a group selected from an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group. Y has a bond to A and B, and further contains a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms (this group has 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atom. (Which may be included) as a substituent. The substituents may be different or the same. Further, Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. X is each independently hydrogen, halogen, carbon number 1
An alkyl group having 15 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or It is an amide group having hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium. 8. The olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is ethylene or two or more olefins containing ethylene. A medical article according to claim 1, or a medical device comprising the same. 9. The molded article for medical use according to claim 8, wherein the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) has a crystal structure derived from an ethylene chain structure. Medical equipment. 10. The medical composition according to claim 1, wherein the aromatic vinyl compound of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is styrene. A molded article or a medical device comprising the same. 11. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)), wherein the diene is divinylbenzene.
A medical molded article according to any one of the preceding claims or a medical device comprising the same. 12. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) having an aromatic vinyl compound content of 5 mol% or more and 50 mol% or less and a diene content of 0.1 mol% or less.
The medical molded article or a medical device comprising the medical molded article according to any one of claims 1 to 11, wherein 0001 mol% or more and 3 mol% or less, the balance being ethylene or two or more olefins containing ethylene. 13. The olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) is ethylene or two or more olefins containing ethylene,
And cross-copolymerized olefin-aromatic vinyl compound-
The diene copolymer (A) has a crystal structure derived from an ethylene chain structure, and the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A)
At least one melting point of 5 ° C or more and 140 ° C or less is observed, and the heat of crystal fusion corresponding to the melting point is 10 J / g or more
The amount is 150 J / g or less.
2. The medical molded article according to any one of 2 or a medical device comprising the molded article. 14. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) having an aromatic vinyl compound content of 5 to 50 mol% and a diene content of 0.0001 to 3 mol%. % Or less, the balance being ethylene or two or more olefins containing ethylene,
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having a crystal structure derived from an ethylene chain structure, and a cross-copolymerized olefin-aromatic vinyl compound-diene 14. The polymer (A) according to any one of claims 1 to 13, wherein at least one of melting points having a crystal fusion heat of 10 J / g or more and 150 J / g or less, which is observed by DSC measurement, satisfies the following relationship. A medical molded article according to claim 1 or a medical device comprising the same. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; The heat of crystal fusion measured by DSC is 10 J / g or more and 1
Melting point (° C.) not more than 50 J / g St: Aromatic vinyl compound content (mol%) 15. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) having an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 to 3 mol%. The medical molded article or a medical device comprising the medical article according to any one of claims 1 to 14, wherein the molar percentage is at most mol%, and the balance is ethylene or two or more olefins containing ethylene. 16. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) having an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 to 3 mol%. The medical molded article or the medical product thereof according to claim 15, wherein the mol% or less, the balance is ethylene or two or more olefins containing ethylene, and the content of the aromatic vinyl compound and the Vicat softening point satisfy the following relationship. Become a medical tool. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 1
40 Tvicat; Vicat softening point (° C) St; Aromatic vinyl compound content (mol%) 17. A thermoplastic resin composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (A) in an amount of 80% by weight or more. A medical article according to claim 1, or a medical device comprising the same. 18. The medical molded article according to claim 1, wherein the thermoplastic resin composition contains an olefin-based polymer and / or a styrene-based polymer. . 19. An olefin polymer comprising high-density polyethylene, low-density polyethylene, ethylene and α having 3 to 8 carbon atoms.
The medical treatment according to claim 18, wherein the medical treatment is any one or more olefin polymers selected from ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, and homopolypropylenes composed of -olefins. Or a medical device comprising the same. 20. A styrene-based polymer comprising polystyrene, rubber-reinforced polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-methacrylic acid ester copolymer, styrene-butadiene random copolymer, 19. The medical molded article according to claim 18, which is at least one selected from a styrene-butadiene block copolymer and a hydrogenated product thereof, and a styrene-isoprene block copolymer and a hydrogenated product thereof. Become a medical tool. 21. The medical composition according to claim 1, wherein the thermoplastic resin composition contains at least one selected from the group consisting of a plasticizer, an anti-fogging agent and an anti-blocking agent. A molded article or a medical device comprising the same. 22. The molded article for medical use according to claim 1, which is a blood bag, an infusion bag or a dialysis bag, or a medical device comprising the same. 23. The medical molded article according to claim 1, wherein the molded article is a tube, a catheter, or a blood circuit. 24. The medical device according to claim 1, wherein the surface of the liquid is provided with antithrombotic properties.