JP5052833B2 - Multilayer body for medical container and medical container - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a medical container having a multilayer body for medical containers and a medical solution container formed from the multilayer body for medical containers.

Examples of resin medical containers used in the medical field include ampoules, vials, syringe containers, and infusion bags made of films. As the resin, polyolefins such as polyethylene and polypropylene, styrene elastomers, vinyl chloride resins, ethylene-vinyl acetate copolymers, cyclic polyolefins, and the like are used.
Among these resins, polyethylene is widely used in medical containers because it is hygienic and flexible, and does not generate toxic gases when incinerated. It is also known that when polyethylene is used for the wetted part, the polyethylene in the chemical solution adsorbs a specific drug such as a fat-soluble vitamin, and the concentration of the specific drug may decrease during storage.

  Therefore, a cyclic polyolefin having a high barrier property such as a reduction in the titer of the drug due to adsorption or absorption of a specific drug, excellent transparency, heat resistance, hygiene, and low water vapor permeability, Widely used as a material for medical containers. As a medical container using a cyclic polyolefin, a prefilled syringe in which a syringe container is filled with a drug in advance is in widespread use.

Patent Document 1 discloses a medical container having a multilayer structure in which a synthetic polyolefin layer or a barrier layer is combined with a cyclic polyolefin layer made of a thermoplastic saturated norbornene-based polymer.
Patent Document 2 is composed of a multilayer film including a surface layer, a flexible layer, a barrier layer, and a seal layer. Cyclic polyolefin and ethylene-α-olefin copolymer are used for the barrier layer, and other layers are mainly used. A medical container using an ethylene-α-olefin copolymer as a component is disclosed.
Patent Document 3 discloses a laminated film in which a B layer made of linear low density polyethylene having a specific melting point and a Vicat softening point is laminated on one or both of the A layer made of a resin such as cyclic polyolefin, and the like. A medical container using is disclosed.
Furthermore, Patent Document 4 discloses a medical treatment using a laminated film in which a base material layer containing a polyolefin resin having a specific melting point as a main component is laminated with a sealant layer containing a cyclic polyolefin resin having a specific glass transition temperature as a main component. A container is described.
Japanese Patent No. 3227709 International Publication No. 03/097355 Pamphlet JP 2004-167800 A JP 2005-254508 A

  However, as described in Paragraph 0027 of Patent Document 1 and Paragraph 0004 of Patent Document 2, cyclic polyolefin has a defect that adhesiveness is poor. Therefore, when manufacturing the multilayer film of patent document 1, there existed a situation which had to use an adhesive agent at the time of lamination | stacking with a cyclic polyolefin layer and another layer. However, in a multilayer film in which an adhesive is used, there is a possibility that components derived from the adhesive bleed out. Therefore, it is not preferable from the viewpoint of hygiene to use such a multilayer film for a medical container, especially for the inner side close to a chemical solution.

  In the technique of Patent Document 2, in order to improve the adhesion of the cyclic polyolefin, an ethylene-α-olefin copolymer is mixed with the cyclic polyolefin to form a barrier layer. However, when an ethylene-α-olefin copolymer is mixed, the barrier property of the barrier layer is lowered, and the drug may be absorbed by the layer adjacent to the barrier layer. Further, when the barrier layer is made thicker in order to improve the decrease in barrier properties, there arises a problem that the flexibility is lowered accordingly.

  In addition, the medical containers described in Patent Documents 3 and 4 have insufficient heat resistance, and are not satisfactory as materials for medical containers that need to be sterilized with high-pressure steam or the like. Moreover, the laminated | multilayer film disclosed by patent document 3 and 4 also had the fault that it was inferior also to blocking resistance.

  The present invention has been made in view of the above circumstances, and without using an adhesive, the innermost layer made of cyclic polyolefin adheres well to other layers, has excellent heat resistance, and is a film. To provide a multilayer body for medical containers with good blocking resistance and a medical container formed from this multilayer body for medical containers and having little deterioration in properties such as transparency and peel strength even when sterilized with high-pressure steam. Let it be an issue.

The multi-layer body for a medical container of the present invention is a multi-layer body for a medical container used for forming a medical container, and is formed so as to be adjacent to the innermost layer made of cyclic polyolefin, and the single-site catalyst. density produced using is composed mainly of linear low density polyethylene which is ^{0.900g / cm 3 ~0.917g / cm 3} , an intermediate layer further contains a high-density polyethylene, containing high-density polyethylene It is characterized by comprising the outermost layer.
The cyclic polyolefin is preferably a hydrogenated product of a ring-opening polymer of a cyclic olefin monomer.
It is preferable that the outermost layer is a mixture of the high-density polyethylene and the high-pressure low-density polyethylene, or is made of only the high-density polyethylene.
The medical container according to the present invention is a medical container provided with a storage unit that stores a chemical solution, and at least the storage unit is formed of the multilayer body for the medical container.
In that case, the multilayer body for medical containers may be a blow molded body. Moreover, the multilayer body for medical containers may be a film, and the housing portion may be formed by hot plate molding of the film or formed in a bag shape.

  According to the present invention, without using an adhesive, the innermost layer made of a cyclic polyolefin adheres well to other layers, has excellent heat resistance, and in the case of a film, has good blocking resistance. It is possible to provide a medical container multilayer body and a medical container which is formed from the medical container multilayer body and has little deterioration in properties such as transparency and peel strength even when sterilized with high-pressure steam or the like.

Hereinafter, the present invention will be described in detail.
The multi-layer body for medical containers according to the present invention is a multi-layer body for medical containers which is used for forming medical containers, and particularly suitable for forming a container for storing a chemical solution among medical containers, and is made of a cyclic polyolefin. An innermost layer, an intermediate layer that is formed adjacent to the innermost layer and is manufactured using a single-site catalyst, and is composed of a linear low-density polyethylene as a main component, and an outermost layer containing a high-density polyethylene At least.

FIG. 1 shows a multilayer body for medical containers (hereinafter referred to as a multilayer body) 10 as an example of the present invention.
The multilayer body 10 of this example includes an innermost layer 11 made of a cyclic polyolefin, an intermediate layer 12 mainly composed of a linear low-density polyethylene produced using a single-site catalyst, and a high-density polyethylene. The outermost layer 13 consists of three layers that are sequentially laminated, and is formed on a film by an air-cooled or water-cooled multilayer inflation molding method, a multilayer T-die molding method, or the like. In the present invention, the film and the sheet are collectively referred to as a film.

The innermost layer 11 is an inner layer when a medical container is formed from the multilayer body 10 and is in direct contact with a chemical solution or the like stored in the medical container, and is formed from a cyclic polyolefin.
Since cyclic polyolefin has little drug adsorption and absorption, it is possible to suppress a decrease in the potency of the drug solution to be accommodated by forming a medical container with the multilayer body 10 having the layer made of cyclic polyolefin as the innermost layer 11. Further, the cyclic polyolefin is suitable as the innermost layer 11 from the viewpoint of having a high barrier property such as low water vapor transmission rate, extremely little impurity elution, and excellent hygiene. Furthermore, since the cyclic polyolefin has heat resistance and transparency, it needs to be sterilized with high-pressure steam or the like, and is suitable for use in a medical container where the contents are desired to be visible from the outside.

Cyclic polyolefins include ring-opening polymers of cyclic olefin monomers, hydrogenated products of the ring-opening polymers, addition polymers of cyclic olefin monomers, and addition copolymerization with other monomers copolymerizable with cyclic olefin monomers. Examples include coalescence. Among these, from the viewpoint of heat resistance, mechanical strength, etc., a hydrogenated product of a ring-opening polymer of a cyclic olefin monomer is preferable. Moreover, since a low adsorptive polymer is obtained, the cyclic olefin monomer which consists only of hydrocarbons is preferable.
Although it does not specifically limit as a cyclic olefin monomer, A norbornene-type monomer, a monocyclic cyclic olefin monomer, etc. are mentioned. The norbornene-based monomer is a monomer having a unit derived from a norbornene structure in the monomer structure, and specifically includes, for example, bicyclo [2.2.1] hept-2-ene (commonly used norbornene), tricyclo [4. 3.0.1 ^2,5 ] deca-3,7-diene (common name dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (conventional Names methanotetrahydrofluorene) and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and the like. Further, these norbornene monomers may have a hydrocarbon group having 1 to 3 carbon atoms. Specific examples of the monocyclic olefin monomer include cyclohexene, cycloheptene, and cyclooctene. These cyclic olefin monomers can be used alone or in combination of two or more.
The ring-opening polymer of a cyclic olefin monomer is obtained by polymerizing a cyclic olefin monomer by a metathesis reaction in the presence of a known ring-opening polymerization catalyst. The hydrogenated product of the ring-opened polymer of the cyclic olefin monomer is obtained by hydrogenating the ring-opened polymer with a known hydrogenation catalyst.
Moreover, as another monomer which can be addition-copolymerized with a cyclic olefin monomer, C2-C20 alpha olefins, such as ethylene, propylene, 1-butene, 1-hexene, are mentioned, for example. These α-olefins can be used alone or in combination of two or more.
The addition (co) polymer of the cyclic olefin monomer can be obtained by polymerization using a known catalyst comprising a titanium, zirconium compound and an organoaluminum compound.

  Among those commercially available as cyclic polyolefins, examples of the addition (co) polymers of cyclic olefin monomers include Apel (registered trademark) manufactured by Mitsui Chemicals, Inc., TOPAS (registered trademark) manufactured by TICONA, and the like. Examples of the hydrogenated product of the ring-opening polymer include ZEONOR (registered trademark) and ZEONEX (registered trademark) manufactured by Nippon Zeon Co., Ltd.

The cyclic polyolefin preferably has a glass transition temperature (hereinafter sometimes referred to as Tg) of 70 ° C to 180 ° C, more preferably 100 ° C to 140 ° C. When Tg is less than 70 ° C., the heat resistance of the medical container formed from the multilayer body 10 is lowered, and may not be suitable for sterilization with high-pressure steam or the like. On the other hand, when Tg exceeds 140 ° C., the moldability and heat sealability of the multilayer body may be reduced. Here, the glass transition temperature is a value measured by a differential scanning calorimeter (hereinafter referred to as DSC) in accordance with JIS K 7121, and is a value described in a manufacturer's catalog and technical data. .
The Tg of the cyclic polyolefin can be arbitrarily adjusted by a method of mixing a plurality of types of cyclic polyolefins having good compatibility at an appropriate ratio. The degree of compatibility of the mixture of cyclic polyolefins can be determined by measuring the Tg of the mixture by DSC. In the case of a mixture with good compatibility, only one Tg is observed, whereas when the compatibility is not good, a plurality of Tg is observed. It is preferable that the mixture has good compatibility because both heat resistance that can withstand the target high-pressure steam sterilization temperature and moldability can be achieved.

The innermost layer 11 is made of a cyclic polyolefin. However, in the range not impairing the effects of the present invention, for example, an antistatic agent, an antioxidant, a lubricant, an antifogging agent, an ultraviolet absorber, and a neutralizing agent. Various additives generally used in the field of resins, etc. may be contained in the normal use range.

The intermediate layer 12 is a layer formed so as to be adjacent to the innermost layer 11 described above, and is manufactured using a single-site catalyst typified by a metallocene catalyst, and has a density of 0.860 g / cm ³ or more and 0. The main component is a linear low density polyethylene (hereinafter sometimes referred to as LLDPE) of less than 940 g / cm ³ . In addition, a main component means that content is 50 mass% or more here.
Such LLDPE produced using a single-site catalyst has excellent adhesion to cyclic polyolefins, and has little decrease in adhesion even when exposed to high temperature and high humidity conditions by high-pressure steam sterilization. Therefore, by providing the intermediate layer 12 mainly composed of LLDPE adjacent to the innermost layer 11 made of cyclic polyolefin, another layer can be adhered favorably and stably via the intermediate layer 12. be able to. In addition, LLDPE produced using a single site catalyst is excellent in transparency, and its deterioration is small even when exposed to high temperature and high humidity conditions. From these points, the multilayer body 10 including the intermediate layer 12 is suitable for forming a medical container that needs to be sterilized by high-pressure steam.

The LLDPE, can be suitably used as long as it is less than the single site catalyst density were prepared using 0.860 g / cm ³ or more 0.940 g / cm ^3, Of these density 0.900 When the one having a thickness of ˜0.917 g / cm ³ is used, a multilayer body 10 and a medical container with better heat resistance can be obtained, and even when sterilized by high-pressure steam at 121 ° C., no trouble occurs, and the multilayer body 10 The decrease in peel strength between the intermediate layer 12 and the innermost layer 11 after sterilizing the medical container formed from high-pressure steam is suppressed. Here, if the density of LLDPE is less than 0.860 g / cm ³ , heat resistance may be reduced. On the other hand, when the density of LLDPE is 0.940 g / cm ³ or more, the transparency and impact resistance of the container may decrease.
Further, as the LLDPE produced using a single site catalyst, a plurality of types having different densities may be used in combination.

  Of the LLDPEs produced with a single-site catalyst, those having a wide composition distribution of ethylene and α-olefin as measured by composition analysis are preferable because of excellent workability and impact resistance. Examples of commercially available products having such characteristics include Harmolex (registered trademark) manufactured by Nippon Polyethylene Co., Ltd., Umerit (registered trademark) manufactured by Ube Industries, Ltd., and Evolution (registered trademark) manufactured by Prime Polymer Co., Ltd. It can be used suitably.

  The intermediate layer 12 contains LLDPE produced by a single site catalyst as a main component, that is, 50% by mass or more, and preferably 65% by mass or more, more preferably 80% by mass or more from the viewpoint of flexibility. Other polyethylenes and cyclic polyolefins may be included as long as the adhesiveness with the innermost layer 11 is not impaired. In particular, when high-density polyethylene having a higher density than LLDPE produced by a single-site catalyst is used in an amount of preferably 30% by mass or less, more preferably 25% by mass or less, heat resistance is improved, and high-pressure steam sterilization is performed. A decrease in the adhesiveness of the intermediate layer 12 is further suppressed. In addition, when other polyethylene or cyclic polyolefin is used in combination with LLDPE as described above, there is an advantage that the multilayer body 10 having an excellent appearance can be easily obtained.

  Further, the intermediate layer 12 is also variously used in the field of resins, such as an antistatic agent, an antioxidant, a lubricant, an antifogging agent, an ultraviolet absorber and a neutralizing agent, as long as the effects of the present invention are not impaired. You may contain the additive in the normal use range.

The outermost layer 13 is the outermost layer when a medical container is formed from the multilayer body 10, and is formed containing high-density polyethylene (hereinafter sometimes referred to as HDPE).
By providing a layer containing HDPE in the outermost layer 13, the heat resistance of the resulting multilayer body 10 is improved, and a medical container with less characteristic deterioration such as deformation of the surface of the medical container is formed by sterilization with high-pressure steam. Can do. In addition, the film-like multilayer body 10 as in the example of FIG. 1 is often wound and rolled to be stored or handled, but a layer containing HDPE is provided in the outermost layer 13. Thus, the blocking resistance of the multilayer body 10 is also excellent.

As HDPE, if it has a density of 0.940-0.970 g / cm ³ , it can be suitably used, but among these, if a density of 0.945-0.970 g / cm ³ is used, The multilayer body 10 excellent in heat resistance and blocking resistance is obtained. Moreover, you may use together multiple types of HDPE from which density differs.

The suitable content of HDPE in the outermost layer 13 varies depending on the density of HDPE. For example, in the case of HDPE having a density of 0.945 to 0.970 g / cm ³ , the content is 20% by mass or more in the outermost layer 13. If present, a sufficiently heat-resistant medical container with little deterioration in characteristics can be formed by sterilization with high-pressure steam at 121 ° C. However, in order to develop more stable heat resistance and blocking resistance, the content of HDPE in the outermost layer 13 is preferably 30% by mass or more, more preferably 70% by mass or more, and further preferably 100% by mass. is there.
However, for the purpose of improving the molding stability, another resin may be used in combination with the outermost layer 13, and in that case, the content of HDPE may be appropriately determined. Examples of such other resins include polyolefins other than HDPE, and polyethylene resins such as linear low density polyethylene and high pressure method low density polyethylene can be preferably used. Among these, when the high pressure method low density polyethylene is used together with HDPE, the molding stability of the outermost layer 13 can be further enhanced. The high-pressure low-density polyethylene preferably has a density of 0.910 to 0.935 g / cm ³ , more preferably 0.920 to 0.935 g / cm ³ .

  In addition, the outermost layer 13 also has various additions commonly used in the resin field, such as an antistatic agent, an antioxidant, a lubricant, an antifogging agent, an ultraviolet absorber, and a neutralizing agent, as long as the effects of the present invention are not impaired. An agent may be contained within a normal use range. In addition, the outermost layer 13 may be one that has been subjected to modification such as crosslinking with an electron beam to improve heat resistance.

Although there is no restriction | limiting in particular in the total thickness of the multilayer body 10, Usually, it is 60-1000 micrometers, and when the softness | flexibility, intensity | strength, etc. of the multilayer body 10 are considered, 100-600 micrometers is preferable and 100-400 micrometers is more preferable.
Although there is no restriction | limiting in particular in the thickness of each layer, It is preferable that the innermost layer 11 is 5-100 micrometers, and the outermost layer 13 is 5-100 micrometers. If the thickness of the innermost layer 11 is less than 5 μm, it may be easy to adsorb the medicine to be accommodated, and if it exceeds 100 μm, the flexibility of the multilayer body 10 and the heat sealability when forming a medical container from the multilayer body 10 May decrease. Moreover, if the thickness of the outermost layer 13 is less than 5 μm, the heat resistance of the multilayer body 10 may be reduced, and if it exceeds 100 μm, the transparency may be reduced.
Therefore, in the case of the multilayer body 10 having three layers, it is preferable that the total thickness is 60 to 1000 μm, the innermost layer 11 is 5 to 100 μm, the outermost layer is 5 to 100 μm, and the rest is the intermediate layer 12.
In addition, when the multilayer body 10 consisting of three layers is a film, it is preferable that the innermost layer 11 is 5 to 100 μm, the intermediate layer 12 is 50 to 300 μm, and the outermost layer is 5 to 100 μm.

  As described above, the multilayer body 10 in FIG. 1 is composed of three layers in which the innermost layer 11 made of cyclic polyolefin and the outermost layer 13 containing HDPE are well bonded via the intermediate layer 12, Although provided with sufficient characteristics as the multilayer body 10 for medical containers, for the purpose of further imparting other characteristics, one or more other layers are provided between the intermediate layer 12 and the outermost layer 13, It is good also as four or more layers. Such layers include gas barrier resin layers such as ethylene-vinyl alcohol copolymer, adhesive resin layers such as ethylene-vinyl acetate copolymer, ultraviolet shielding layers such as polyolefin resin containing iron oxide, xylylene range Examples thereof include an oxygen absorption layer composed of a polyamide resin such as MXD nylon obtained from an amine and an α, ω-linear aliphatic dibasic acid such as adipic acid and a cobalt salt.

  Further, as a form of the multilayer body, not only the multilayer body 10 formed in a film as shown in FIG. 1, but also a blow molded body molded by a multilayer blow molding method (multilayer hollow molding method) as will be described in detail later. A three-dimensional multilayer body may be used.

The medical container of this invention is a medical container provided with the accommodating part which accommodates a chemical | medical solution, Comprising: At least an accommodating part consists of the above-mentioned multilayer body. In that case, it arrange | positions so that an innermost layer may become an inner side of an accommodating part and an outermost layer may become an outer side. In addition, the medical container is usually provided with a port portion serving as a drug solution inlet in addition to the accommodating portion.
Hereinafter, the specific example of the medical container of this invention is demonstrated using drawing.

FIG. 2 shows a medical container 20 in which a housing portion 21 and a port portion 22 are integrally formed by a multilayer blow molding method. The upper part of the medical container 20 is a suspending part 23 in which a suspending hole is formed, and the lower port part 22 is connected to the innermost layer 11 and the outer peripheral part of a cylindrical rubber material through which an injection needle can be inserted. A rubber plug 22a provided with a weldable synthetic resin by an injection molding method is attached to be sealed.
The medical container 20 can be manufactured by a normal multilayer blow molding method using a multilayer blow molding machine. That is, after extruding a multilayer parison and sandwiching the multilayer parison with a mold, clean air may be blown into the multilayer parison. Here, by using a mold that can integrally mold the accommodating portion 21 and the port portion 22, the medical container 20 of FIG. 2 made of a hollow blow-molded body can be formed. In addition, when the multilayer parison is sandwiched between molds, the mold is pre-blowed with clean air in advance, and after closing the mold, the mold is made negative pressure through a vacuum hole formed in the mold. Transfer accuracy can be improved.

  As a method of forming the port portion, in addition to the method of integrally forming with the housing portion by the multilayer blow molding method, for example, as shown in the example of FIG. Examples thereof include a method of heat sealing and a method of integrating at the same time as molding by insert blow molding with a cylindrical member inserted. When these cylindrical members are used, the rubber plug 22a is attached to the cylindrical member for sealing, and the details will be described later with reference to FIG. After that, the lid member and the cylindrical member may be sealed by a method of welding the ultrasonic wave or the like so that the peripheral portion of the rubber stopper is further suppressed by a ring-shaped lid member.

FIG. 3 (A) shows a medical container 30 that includes an accommodating portion 31 formed by hot plate molding and a port portion 32 that is made of a cylindrical member and can be sealed by heat sealing a rubber plug 32a. It is a thing. The container 31 of the medical container 30 is formed by stacking two film molded articles 10 ′ shown in FIG. 4 and heat-sealing the peripheral edge 33.
That is, when this medical container 30 is manufactured, first, along the inner shape of the accommodating portion 31 at the center of the film-like multilayer body 10 as shown in FIG. 1 by hot plate forming such as vacuum forming or pressure forming. A concave portion is formed to obtain a film molded product 10 ′ as shown in FIG. Then, two film molded products 10 ′ are prepared and are stacked so that the concave portions face each other. And the peripheral part of two film molded product 10 'is heat-sealed, arrange | positioning a cylindrical member in a predetermined position. The heat sealing temperature is not particularly limited because it depends on the total thickness of the multilayer body 10, but is preferably about 150 to 280 ° C. Moreover, you may trim a peripheral part after heat sealing as needed. According to such a method, the medical container 30 shown in FIG. 3A can be manufactured by simultaneously forming the housing portion 31 and forming the port portion 32 by heat sealing the cylindrical member.
The formation of the accommodating portion 31 and the formation of the port portion 32 may be performed in separate steps.

  As the material of the cylindrical member forming the port portion 32, the same cyclic polyolefin as the innermost layer 11 of the multilayer body 10 is preferable because the heat sealability with the accommodating portion 31 is good. As long as it can be heat-sealed closely, it is not limited to cyclic polyolefin, LLDPE manufactured with a single-site catalyst, the same composition as the intermediate layer 12, and the like can also be used. Moreover, the multilayer thing which used resin which can be heat-sealed for the heat-seal surface of a cylinder member may be used. Here, instead of forming the port portion 32 from the cylindrical member and the rubber plug 32a, as shown in FIG. 3B, after the rubber plug 32b is loaded into the cylindrical member, the ring-shaped lid member 32c is used. The lid member 32c and the cylindrical member may be welded by ultrasonic waves or the like so as to press the peripheral edge of the rubber plug 32b.

FIG. 5 shows a so-called film bag type medical container 40 provided with a housing part 41 in which the film-like multilayer body 10 as shown in FIG. 1 is formed in a bag shape and a port part 42 made of a cylindrical member.
The medical container 40 of this example uses a multilayer body formed in a cylindrical shape by a multilayer inflation method or the like, heat seals both end portions thereof to form a housing portion 41, and a cylindrical member at a predetermined position on one end thereof Can be manufactured by a method of forming a suspended portion at the other end. The heat sealing of both end portions and the heat sealing of the cylindrical member may be performed simultaneously or in separate steps. Further, instead of using a cylindrical multilayer body, the multilayered body 10 as shown in FIG. 1 may be used, and after superposing them, the housing part may be formed by heat sealing the peripheral part. .
Further, in this example, the port portion 42 includes a cylindrical member formed of LLDPE or the like manufactured using a cyclic polyolefin or a single site catalyst, a rubber plug 42a through which an injection needle can be inserted, and a peripheral portion of the rubber plug 42a. It is closed by a ring-shaped lid member 42b for pressing.

  According to the medical container described above, at least the housing part is an innermost layer made of cyclic polyolefin, an intermediate layer mainly composed of linear low-density polyethylene manufactured using a single-site catalyst, and a high density Since it is formed from a multilayer body with an outermost layer containing polyethylene, each layer is well bonded, hygienic, excellent in heat resistance, and transparent even when autoclaved There is little deterioration in properties such as peel strength.

In addition, as a form of a medical container, it is not limited to the form provided with one accommodating part, for example, as shown in FIG. 6, the accommodating part 51 is divided into a plurality by a partition wall seal part 52 that can communicate, The multi-chamber medical container 50 which can store a chemical | medical solution separately may be sufficient.
The multi-chamber medical container 50 of FIG. 6 is provided with a partition seal portion 52 along the width direction of the storage portion 51 formed in a bag shape, and the storage portion 51 is connected to the first storage portion 51a and the second storage portion 51b. It has been divided. When the multi-chamber medical container 50 is used, the partition wall seal portion 52 is peeled off when the user presses the first housing portion 51a or the second housing portion 51b from the outside, and the second liquid medicine and the second medical solution in the first housing portion 51a. The chemical solution in the container 51b is mixed.
There is no restriction | limiting in the formation method of the partition seal | sticker part 52, For example, when heat sealing is implemented at the time of formation of the accommodating part 51, you may heat-seal and form simultaneously with it. In addition to heat sealing, a known sealing method such as impulse sealing may be performed separately. Further, in the case where the accommodating portion 51 is manufactured by blow molding, a mechanism for forming the partition seal portion 52 is provided in a mold used at the time of blow molding so that the partition seal portion 52 can be formed simultaneously with blow molding. May be.

Furthermore, although illustration is omitted, the medical container of the present invention may be provided with a light-shielding layer on the outside thereof, particularly on the outside of the housing portion, for protecting the drug solution as necessary. Examples of suitable materials for the light shielding layer include metal foils such as aluminum foil, aluminum vapor deposition films, laminate films of metal foils and synthetic resin films, and synthetic resin films containing pigments. Among these light-shielding layers, aluminum foil and aluminum vapor-deposited film have not only light-shielding properties, but also moisture-proof, oil-resistant, non-water-absorbing properties, etc., and improve the long-term storage stability of chemicals stored in medical containers. It is preferable from the point. Further, such a light shielding layer may be provided so as to be peelable from the medical container so that the medical solution can be visually observed from the outside when the medical container is used.
As mentioned above, although the chemical | medical solution was demonstrated as an example as a chemical | medical agent accommodated in the medical container of this invention, the chemical | medical agent which consists of powder agents, such as not only a chemical | medical solution but antibiotics, may be sufficient. Specific examples of the chemical solution include, but are not limited to, chemical solutions used as injections such as physiological saline, circulatory system drugs, contrast agents, and antibacterial agents.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to a following example.
[Example 1]
The medical container 20 of FIG. 2 filled with 100 ml of water was manufactured as follows.
First, a blow molded article having a three-layer structure in which an innermost layer having a thickness of 30 μm, an intermediate layer having a thickness of 250 μm, and an outermost layer having a thickness of 20 μm are sequentially laminated by a multilayer blow molding method using a multilayer blow molding machine. The accommodating part 21 and the port part 22 were integrally molded. Next, 100 ml of water was filled into the accommodating portion 21 from the port portion 22, and then the rubber plug 22 a was heat sealed to the port portion 22 to seal the medical container 20. The rubber plug 22a has a melt flow rate at 280 ° C. (hereinafter referred to as “MFR”) in accordance with ISO 1133 on the outer periphery, and the load at the time of MFR measurement in the examples and comparative examples is all 21.18N. ) Is 17 g / 10 min and a glass transition temperature of 136 ° C. is used, which is provided with a layer made of a cyclic polyolefin “ZEONEX (manufactured by ZEON CORPORATION)” (hereinafter referred to as “COP1”) by an injection molding method. did.

The innermost layer is a cyclic polyolefin “ZEONOR 1020R (manufactured by Zeon Corporation)” (hereinafter referred to as “Zeon Corporation”) having an MFR of 20 g / 10 minutes at 280 ° C. and a glass transition temperature of 102 ° C. in accordance with COP1 and ISO 1133. "COP2") in a 1: 1 mass ratio was used. Only one Tg of this mixed cyclic polyolefin was observed and was 119 ° C.
The intermediate layer is an LLDPE manufactured with a single site catalyst (hereinafter sometimes referred to as a single site LLDPE), and has an MFR at 190 ° C. of 1 g / 10 min and a density of 0.906 g / cm ³ . A certain “Harmorex (manufactured by Nippon Polyethylene Co., Ltd.)” and HDPE “Novatec (manufactured by Nippon Polyethylene Co., Ltd.)” having an MFR at 190 ° C. of 3.5 g / 10 min and a density of 0.956 g / cm ³ are 8: What was blended at a mass ratio of 2 was used.
For the outermost layer, HDPE “NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)” having an MFR at 190 ° C. of 3.5 g / 10 min and a density of 0.955 g / cm ³ was used.

The medical container 20 of FIG. 2 filled with water thus obtained was subjected to high-pressure steam sterilization at 121 ° C. for 30 minutes by spray-type high-pressure steam sterilization, and the characteristics before and after the evaluation were evaluated as follows. The evaluation results are shown in the table.
In Examples and Comparative Examples, blocking resistance and molding stability are evaluated only in the case of forming from a film and forming a housing portion, and forming the housing portion from multilayer blow molding as in Example 1. If you do not go.

(Evaluation method)
(1) Blocking resistance Two 10 cm × 10 cm multi-layer bodies were superposed so that their outermost layers were in contact with each other, and a load of 98 N / 100 cm ² was applied thereon and maintained at 60 ° C. for 24 hours. Then, after cooling to room temperature and removing the load, the two films were peeled off. The state of peeling at this time was evaluated in the following two stages.
○: Easy to peel off.
X: There is resistance to peeling.
(2) Peel strength A strip-shaped sample S having a width of 15 mm is cut out from a medical container before and after high-pressure steam sterilization, and a JIS between the innermost layer 11 and the intermediate layer 12 as schematically shown in FIG. The T-shaped peel strength according to K6854-3 was measured at a tensile speed of 300 mm / min. The test was conducted with a tensile tester. Reference symbol P in the figure indicates a chuck of a tensile tester.
As shown in FIG. 7A, in order to bring the sample S into a state in which only the innermost layer 11 is broken at the broken portion V, first, as shown in the plan view of FIG. Cuts C are made at two positions facing each other at both ends in the width direction of the sample S cut out from, and the sample S is pulled in the length direction as indicated by arrows in FIG. 7B. Then, only the innermost layer 11 is completely broken at the notch C, and the other layers are not broken. Therefore, by setting this in a tensile tester, the peel strength at the interface between the innermost layer 11 and the intermediate layer 12 can be measured as shown in FIG.
(3) Transparency The haze before and after high-pressure steam sterilization was measured according to JIS K7136.
(4) Heat resistance A medical container placed on a punched metal tray with a round hole was autoclaved with a spray-type high-pressure steam sterilizer, and the appearance of the medical container was visually evaluated.
○: No deformation or shrinkage after sterilization.
Δ: Some deformation shrinkage such as surface roughness.
X: There is a round hole tray trace or the like that is greatly deformed or contracted.
(5) Molding stability The shape stability of the tube-shaped film during inflation molding and the occurrence of wrinkles on the film were evaluated.
○: The tube shape is constant. No wrinkles were found on the film.
X: The tube shape is unstable and the tube diameter varies. The film was partially wrinkled.

[Example 2]
A medical container 20 was obtained in the same manner as in Example 1 except that the composition of the outermost layer and the configuration of the port portion 22 were changed.
The outermost layer includes a high pressure method low density polyethylene “NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)” having an MFR at 190 ° C. of 1.1 g / 10 min and a density of 0.927 g / cm ³ , and an MFR at 190 ° C. of 3 A high-density polyethylene “Novatec (manufactured by Nippon Polyethylene Co., Ltd.)” having a density of 0.956 g / cm ³ at 0.5 g / 10 minutes and dry blended at a mass ratio of 7: 3 was used.
The port portion 22 is a cylindrical member made of cyclic polyolefin manufactured by injection molding, heated with a preheating mold set at 250 ° C., and then inserted into the port portion 22 side of the accommodating portion 21 made of the blow molded body of FIG. It was configured by heat sealing at 220 ° C. and mounting. Also, after filling with 100 mL of water, the rubber plug was loaded into the cylindrical member, and then the ring-shaped lid member was placed so as to press the peripheral edge of the rubber plug, and the cylindrical member and the lid member were ultrasonically welded. . In addition, COP1 was used for the cylinder member and the lid member. Evaluation was performed in the same manner as in Example 1. The results are shown in the table.

[Example 3]
A medical container 20 was obtained and evaluated in the same manner as in Example 1 except that only COP2 was used for forming the innermost layer. The results are shown in the table.
In the present embodiment, the rubber plug 22a is used in which a layer made of LLDPE used as an intermediate layer is provided on the outer peripheral portion by an injection molding method.

[ Reference Example 4 ]
In addition to the formation of the intermediate layer, only a single-site LLDPE “Harmolex (manufactured by Nippon Polyethylene Co., Ltd.)” having an MFR at 190 ° C. of 3.5 g / 10 min and a density of 0.918 g / cm ³ was used. Obtained the medical container 20 like Example 3, and evaluated it similarly. The results are shown in the table.
In this example , a rubber plug 22a having a layer made of LLDPE used as an intermediate layer on the outer peripheral portion by an injection molding method was used.

[ Reference Example 5 ]
The intermediate layer was formed except that only a single-site LLDPE “Umerit” (manufactured by Ube Industries) with an MFR at 190 ° C. of 4.0 g / 10 min and a density of 0.931 g / cm ³ was used. In the same manner as in Example 3, a medical container 20 was obtained and evaluated in the same manner. The results are shown in the table.
In this example , a rubber plug 22a having a layer made of LLDPE used as an intermediate layer on the outer peripheral portion by an injection molding method was used.

[Example 6]
For the formation of the intermediate layer, a single-site LLDPE “Umerit 0520F (manufactured by Ube Industries)” having an MFR at 190 ° C. of 2.0 g / 10 min and a density of 0.904 g / cm ³ and an MFR at 190 ° C. Similar to Example 1 except that HDPE “NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)” having a density of 0.956 g / cm ³ at 3.5 g / 10 minutes and blended at a mass ratio of 8: 2 was used. A medical container 20 was obtained and evaluated in the same manner. The results are shown in the table.
In the present embodiment, a rubber plug 22a having a COP1 layer formed on the outer peripheral portion by an injection molding method was used.

[Example 7]
The medical container 30 of FIG. 3 filled with 100 ml of water was manufactured as follows.
First, by a multilayer inflation method using a multilayer inflation film molding machine, an inflation film composed of three layers in which an innermost layer having a thickness of 10 μm, an intermediate layer having a thickness of 220 μm, and an outermost layer having a thickness of 20 μm were sequentially laminated was manufactured. .
Next, the film piece obtained by cutting the blown film was softened by radiant heating with a heater set at 300 ° C., and molded with a vacuum molding machine using a normal temperature mold, and the film molded product 10 ′ of FIG. Got.
Then, two pieces of this film molded product 10 ′ are overlapped so that the concave portions face each other, the peripheral portion is heat sealed, and then the cylindrical member which is an injection molded product of cyclic polyolefin is heat sealed to form the port portion 32. .
Next, after filling the accommodating portion 31 from the port portion 32 with 100 ml of water, as shown in FIG. 3B, the rubber plug 32b is loaded into the cylindrical member, and then the ring-shaped lid member 32c is further inserted into the rubber plug 32b. The cylinder member and the lid member 32c were ultrasonically welded so as to press down the peripheral edge portion. In addition, COP1 was used for the cylinder member and the lid member 32c.

In addition, the same resin as Example 1 was used for the innermost layer, the intermediate layer, and the outermost layer.
Then, the sealed medical container 30 was evaluated. The results are shown in the table.

[Example 8]
The medical container 40 of FIG. 5 filled with 100 ml of water was manufactured as follows.
First, an inflation film having a three-layer structure was produced in the same manner as in Example 7.
Next, both ends of this inflation film are heat-sealed to form a bag, and a cylindrical member, which is an injection-molded product of COP2, is heat-sealed at one end to form a port portion 42 in the film bag-type container 41. did.
Next, after filling 100 ml of water from the port portion 42 into the accommodating portion 41, the rubber plug 42a is loaded into the cylindrical member, and then the ring-shaped lid member 42b is arranged so as to press the peripheral edge of the rubber plug 42a, The cylinder member and the lid member 42b were ultrasonically welded. In addition, COP1 was used for the cylinder member and the cover member 42b.
Then, the sealed medical container 40 was evaluated. The results are shown in the table.

[Example 9]
In the outermost layer, a high-pressure low-density polyethylene “Novatech (manufactured by Nippon Polyethylene Co., Ltd.)” having an MFR at 190 ° C. of 1.1 g / 10 min and a density of 0.927 g / cm ³ , and an MFR at 190 ° C. of 3. The same as Example 8 except that a blend of high density polyethylene “Novatec (manufactured by Nippon Polyethylene Co., Ltd.)” having a density of 0.956 g / cm ³ at 5 g / 10 minutes and a mass ratio of 7: 3 was used. A medical container 20 was obtained and evaluated in the same manner. The results are shown in the table.

[Example 10]
A linear low density polyethylene “NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)” produced using a Ziegler catalyst having an MFR at 190 ° C. of 2.0 g / 10 min and a density of 0.936 g / cm ³ at the outermost layer. And a high-density polyethylene “NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)” having a MFR at 190 ° C. of 3.5 g / 10 min and a density of 0.956 g / cm ³ , blended at a mass ratio of 7: 3. Except that, the medical container 20 was obtained in the same manner as in Example 8 and evaluated in the same manner. The results are shown in the table.

[Comparative Example 1]
In Example 1, as a main component of the intermediate layer, a Ziegler catalyst having an MFR at 190 ° C. of 1.1 g / 10 minutes and a density of 0.906 g / cm ³ was used instead of the single-site LLDPE. The medical container was molded and evaluated in the same manner as in Example 1 except that LLDPE (manufactured by Nippon Polyethylene Co., Ltd.) was used. The evaluation results are shown in the table.

[Comparative Example 2]
For the formation of the intermediate layer, only LLDPE “Moretec (manufactured by Prime Polymer Co., Ltd.)” produced using a Ziegler catalyst with an MFR at 190 ° C. of 2.0 g / 10 min and a density of 0.920 g / cm ³ was used. Except for the above, the medical container was molded and evaluated in the same manner as in Example 1. The evaluation results are shown in the table.

[Comparative Example 3]
The medical container was molded and evaluated in the same manner as in Example 1 except that the outermost layer was not formed and a two-layer structure of the innermost layer and the intermediate layer was used. The evaluation results are shown in the table.

[Comparative Example 4]
For the formation of the outermost layer, LLDPE manufactured by using a Ziegler catalyst having an MFR at 190 ° C. of 2.0 g / 10 min and a density of 0.920 g / cm ³ instead of HDPE “moretech (manufactured by Prime Polymer Co., Ltd.) The medical container was molded and evaluated in the same manner as in Example 1 except that only “)” was used. The evaluation results are shown in the table.

[Comparative Example 5]
For the formation of the outermost layer, LLDPE manufactured by using a Ziegler catalyst having an MFR at 190 ° C. of 2.0 g / 10 min and a density of 0.920 g / cm ³ instead of HDPE “moretech (manufactured by Prime Polymer Co., Ltd.) The medical container was molded and evaluated in the same manner as in Example 8, except that “)” was used. The evaluation results are shown in the table.

In Examples 1 to 3 and 6 to 10 in which single-site LLDPE is used as a main component of the intermediate layer and HDPE is used in combination, a decrease in peel strength and transparency due to high-pressure steam sterilization is suppressed, and heat resistance is also improved. An excellent medical container was obtained. On the other hand, the medical container obtained in Comparative Example 1 in which Ziegler-based LLDPE was used in combination with HDPE had a great decrease in peel strength and transparency due to high-pressure steam sterilization. A similar tendency was observed when Reference Examples 4 and 5 using only a single-site LLDPE for the intermediate layer were compared with Comparative Example 2 using only a Ziegler LLDPE.
In Comparative Example 3 in which the outermost layer was not provided, the transparency was greatly reduced by high-pressure steam sterilization, and the heat resistance was also poor. In Comparative Examples 4 and 5 in which the outermost layer did not contain HDPE, the same tendency as in Comparative Example 3 was observed. In Examples 9 and 10 in which high-pressure low-density polyethylene was used in combination with HDPE as a component of the outermost layer, molding stability was superior to Examples 7 and 8 in which the outermost layer was only HDPE.
Furthermore, in Example 8, the blocking resistance of the film was good, but in Comparative Example 5, it was poor.

It is sectional drawing which shows an example of the multilayer body of this invention. (A) The top view which shows an example of the medical container of this invention, and sectional drawing which follows the I-I 'line of (B) (A). (A) The top view which shows another example of the medical container of this invention, (B) The top view which shows another example of a port part. It is the (A) front view and (B) side view of the film molded product used when manufacturing the medical container of FIG. It is a top view which shows another example of the medical container of this invention. It is a top view which shows the multi-chamber medical container which is an example of the medical container of this invention. It is a top view explaining the manufacturing method of the sample used for (A) schematic diagram explaining the peeling test of an Example, and (B) (A).

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Multilayer body 11 Innermost layer 12 Middle layer 13 Outermost layer 20, 30, 40 Medical container 50 Multiple-chamber medical container

Claims (6)

A multi-layer body for a medical container used for forming a medical container,
An innermost layer made of cyclic polyolefin;
Is formed so as to be adjacent to the innermost layer, the density produced using a single site catalyst is composed mainly of linear low density polyethylene which is ^{0.900g / cm 3 ~0.917g / cm 3} , An intermediate layer further comprising high density polyethylene;
A multilayer body for medical containers, comprising an outermost layer containing high-density polyethylene.   The said cyclic polyolefin is the hydrogenated product of the ring-opening polymer of a cyclic olefin monomer, The multilayer body for medical containers of Claim 1 characterized by the above-mentioned. 3. The multilayer body for a medical container according to claim 1 , wherein the outermost layer is a mixture of the high-density polyethylene and the high-pressure low-density polyethylene. The said outermost layer consists only of the said high density polyethylene, The multilayer body for medical containers in any one of Claim 1 or 2 characterized by the above-mentioned. A medical container having a container for containing a chemical solution,
At least the said accommodating part consists of a multilayer body for medical containers in any one of Claim 1 thru | or 4 , The medical container characterized by the above-mentioned. The medical container multilayer body is a blow molded body or a film,
When the medical container multilayer body is a film, wherein said accommodating portion, said film or those molded hot plate, or the film is characterized in that formed in a bag shape Item 6. A medical container according to Item 5 .

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