TWI437984B - Multilayer body for medical container and medical container - Google Patents

Description

Multi-layer body and medical container for medical container

The present invention relates to a multilayer body for a medical container and a medical container having the drug solution storage portion formed by the multilayer body for the medical container.

The medical container made of resin used in the medical field includes an ampoule (ampule), a vial (vial), an injection container, and an infusion bag formed of a film. Further, as the resin, a polyolefin such as polyethylene or polypropylene, a styrene-based elastomer, a vinyl chloride resin, an ethylene-vinyl acetate copolymer, or a cyclic polyolefin is used.

Among these resins, polyethylene is widely used in medical containers because it is hygienic and soft, and does not generate toxic gases when burned, but on the other hand, it is connected to medical liquids in medical containers. In the liquid portion, when polyethylene is used, the polyethylene in the chemical solution adsorbs a specific drug such as fat-soluble vitamin, and it is found that the concentration of the specific drug may decrease during storage.

Therefore, it is possible to suppress the decrease in the effectiveness of the drug due to the adsorption or absorption of a specific drug, and it is excellent in transparency, heat resistance, hygiene, and the like, and further has a highly resistant cyclic polyolefin such as a low water vapor transmission rate. Materials used as medical containers are gradually being widely used. In a medical container using a cyclic polyolefin, a pre-filled syringe in which a drug is filled in a syringe container in advance is being popularized.

Further, Patent Document 1 discloses that the ice is saturated by thermoplasticity. The cyclic polyolefin layer formed of the olefinic monomer is a multilayer medical container in which a synthetic resin layer or a barrier layer is combined.

Patent Document 2 discloses that a multilayer film including a surface layer, a soft layer, a barrier layer, and a sealing layer is used, and a cyclic polyolefin and an ethylene-α-ene copolymer are used for the barrier layer, and ethylene-α- is used for the other layer. A medical container in which an olefin copolymer is a main component.

Patent Document 3 discloses that a single layer or both surfaces of the layer A formed of a resin such as a cyclic polyolefin is laminated with a linear type having a specific melting point and a Vicat softening point. A laminated film of layer B formed of density polyethylene, and a medical container using the same.

Further, Patent Document 4 discloses that a base material layer containing a polyolefin-based resin containing a specific melting point as a main component is laminated with a cyclic polyolefin-based resin having a specific glass transition temperature as a main component. A medical container for laminating a film of a layer.

[Patent Document 1] Japanese Patent No. 3227709 [Patent Document 2] International Patent Publication No. 03/097355 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-167800 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-254508

However, as described in paragraph 0027 of Patent Document 1 or paragraph 0004 of Patent Document 2, the cyclic polyolefin has a drawback that the adhesion is not good. Therefore, in the case of manufacturing the multilayer film of Patent Document 1, the cyclic polyolefin layer When laminating with other layers, there is a case where an adhesive has to be used. However, in the use of the multilayer film, there is a possibility that the component derived from the adhesive is released. Therefore, if such a multilayer film is used for a medical container, particularly for use in the vicinity of the drug solution, it is not suitable from the viewpoint of hygiene.

In the technique of Patent Document 2, in order to improve the adhesion of the cyclic polyolefin, an ethylene-α-ene copolymer is mixed with a cyclic polyolefin to form a barrier layer. However, when the ethylene-α-ene copolymer is mixed, the barrier property of the barrier layer is lowered, and the agent is absorbed by the layer adjacent to the barrier layer. Further, when it is desired to improve the barrier property and increase the barrier layer, there is a problem that the flexibility is lowered.

Further, the medical container described in Patent Document 3 or 4 has insufficient heat resistance and cannot satisfy the material of a medical container that requires high-pressure steam to be sterilized. Further, the laminated film disclosed in Patent Document 3 or 4 has a disadvantage that the barrier property is not good.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an innermost layer formed of a cyclic polyolefin and a good layer which are excellent in heat resistance without using an adhesive, and in the case of a film, A multilayer container for a medical container which is excellent in barrier properties, and a medical container which is formed of a multilayer body for a medical container and which is sterilized by high-pressure steam or the like, and which has little deterioration in characteristics such as transparency and peel strength.

The multilayer body for medical containers of the present invention is used in the form of a medical container A multilayer body for a medical container characterized by having at least an innermost layer formed of a cyclic polyolefin, and an adjacent innermost layer formed by using a single-site catalyst The intermediate layer of the linear low-density polyethylene produced as a main component; and the outermost layer containing high-density polyethylene.

The cyclic polyolefin is preferably a hydrogen additive of a ring-opening polymer of a cyclic olefin monomer.

The linear low-density polyethylene has a density of 0.860 g/cm ³ or more and less than 0.940 g/cm ³ .

The density of the aforementioned high density polyethylene is from 0.940 to 0.970 g/cm ³ .

The outermost layer is a mixture of the aforementioned high-density polyethylene and high-pressure process low-density polyethylene, or is formed only of the aforementioned high-density polyethylene.

The multilayer body for a medical container of the present invention has a total thickness of 60 to 1000 μm, and is composed of the innermost layer having a thickness of 5 to 100 μm, the intermediate layer, and the outermost layer of the outermost layer having a thickness of 5 to 100 μm. Formed.

The medical container according to the present invention is a medical container including a housing portion for storing a chemical liquid, characterized in that at least the storage portion is formed of the multilayer body for a medical container.

In this case, the multilayer body for a medical container may be a blow molded body.

According to the present invention, it can be provided that the ring is not used even if an adhesive is not used The inner layer formed of the polyolefin is excellent in heat resistance, and is excellent in heat resistance, and in the case of a film, a multilayer body for a medical container having excellent barrier properties; and the multilayer body for a medical container It is formed into a medical container which is less deteriorated in characteristics such as transparency and peel strength even when sterilized by high-pressure steam.

Hereinafter, the present invention will be described in detail.

The multilayer body for a medical container according to the present invention is used for forming a medical container, and is particularly suitable for use in forming a housing portion for storing a chemical solution in a medical container, and has at least an innermost layer formed of a cyclic polyolefin. And an intermediate layer formed by adjoining the innermost layer and having a linear low-density polyethylene produced by using a single-site catalyst, and an outer layer containing high-density polyethylene .

Fig. 1 shows a multilayer body (hereinafter referred to as a multilayer body) 10 for a medical container according to an example of the present invention.

The multilayer body 10 of this example is composed of: an innermost layer 11 formed of a cyclic polyolefin; and an intermediate layer 12 mainly composed of a linear low-density polyethylene produced by using a single activated site catalyst; The outermost layer 13 containing the high-density polyethylene is formed by three layers laminated in this order, and is formed into a film by a multilayer expansion molding method such as air cooling or water cooling, a multilayer T-die molding method, or the like. Further, in the present invention, the film and the sheet are collectively referred to as a film.

When the medical container is formed from the multilayer body 10, the innermost layer 11 is a layer that is in contact with the chemical solution or the like contained in the medical container. Formed by a polyolefin.

In the cyclic polyolefin, since the adsorption or absorption of the drug is small, the medical container is formed by forming the layer formed of the cyclic polyolefin as the multilayer body 10 of the innermost layer 11, and the effectiveness of the contained chemical solution can be suppressed from being lowered. Further, the cyclic polyolefin has high barrier properties such as low water vapor transmission rate and extremely little elution of impurities, and is most suitable as the innermost layer 11 from the viewpoint of excellent hygiene. Further, the cyclic polyolefin has heat resistance and transparency, and is also suitable for use in a medical container which is required to be sterilized by high-pressure steam or the like and which is desired to visually view the contents from the outside.

The cyclic polyolefin may be a ring-opening polymer of a cyclic olefin monomer and a hydrogen additive of the ring-opening polymer, and further, an additional polymer of a cyclic olefin monomer and a copolymerizable with a cyclic olefin monomer. Additional copolymers of other monomers, and the like. Among these, from the viewpoints of heat resistance, mechanical strength, and the like, a hydrogen additive of a ring-opening polymer of a cyclic olefin monomer is preferred. Further, from the viewpoint of obtaining a polymer having low adsorptivity, a cyclic olefin monomer formed only of hydrogen carbide is preferred.

The cyclic olefin monomer is not particularly limited, and examples thereof include a norbornene-based monomer and a monocyclic olefin monomer. The norbornene-based single system has a monomer derived from a unit of a norbornene structure in a monomer structure, specifically, for example, bicyclo [2.2.1] hep-2-ene (common name: norbornene), three Ring [4.3.0.1 ^2.5 ] Dec-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 ^2,5 ] deca-3-ene (conventional name: Methane tetrahydroanthracene) and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene). Further, these norbornene monomers may have a hydrocarbon group of carbon 1-3. Specific examples of the monocyclic olefin monomer include cyclohexene, cycloheptene, and cyclooctene. These cyclic olefin monomers may 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 substitution reaction in the presence of a known ring-opening polymerization catalyst. Further, the hydrogen addition product of the ring-opening polymer of the cyclic olefin monomer is obtained by hydrogenating the ring-opening polymer by a known hydrogenation catalyst.

Further, as another monomer which can be additionally copolymerized with the cyclic olefin monomer, for example, an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene or 1-hexene can be mentioned. These α-olefins may be used alone or in combination of two or more. The additional (co)polymer of the cyclic olefin monomer can be obtained by polymerization using a catalyst formed of a well-known titanium, zirconium compound and an organoaluminum compound.

In the case of the commercially available cyclic polyolefin, the additional (co)polymer of the cyclic olefin monomer, Abel (registered trademark) manufactured by Mitsui Chemicals Co., Ltd., and TOPAS (registered trademark) manufactured by TICONA Co., Ltd. In the hydrogen addition of the ring-opening polymer of the cyclic olefin monomer, ZEONOA (registered trademark) and ZEONEX (registered trademark) manufactured by ZEON Co., Ltd., Japan, and the like are mentioned.

The cyclic polyolefin is preferably a glass transition temperature (hereinafter, also referred to as Tg) of 70 ° C to 180 ° C, more preferably 100 ° C to 140 ° C, and a Tg less than 70 ° C. The medical container formed by 10 has low heat resistance and may not be sterilized by high pressure steam or the like. On the other hand, when the Tg exceeds 140 ° C, the formability of the multilayer body or the sheet sealability is lowered. In addition, the glass transition temperature here is measured by a differential scanning calorimeter (hereinafter referred to as DSC) in accordance with JIS K 7121. The value is the value of the catalogue and technical data recorded in the manufacturing company.

The Tg of the cyclic polyolefin can be arbitrarily adjusted by a method of mixing a plurality of cyclic polyolefins at a suitable ratio to obtain a good compatibility. The degree of compatibility of the mixture of cyclic polyolefins can be known by measuring the Tg of the mixture by DSC. In the case of a mixture having a good compatibility, only one Tg can be observed, and in the case where the compatibility cannot be said to be good, a plurality of Tg can be observed. In the case of a mixture having good compatibility, the heat resistance and moldability against the autoclave sterilization temperature can be achieved, which is preferable.

In addition, although the innermost layer 11 is formed of a cyclic polyolefin, it may contain a charging inhibitor, an oxidation inhibitor, a lubricant, or the like within a normal range of use, without departing from the effects of the present invention. Anti-fuzzing agents, ultraviolet absorbers, neutralizers, and the like, various additives generally used in the field of resins.

The intermediate layer 12 is formed by a single active site catalyst represented by a metallocene catalyst, and is formed by a single active site catalyst represented by a metallocene catalyst, and has a density of 0.860 g/cm ³ or more and 0.940 g/cm ^{3 .} The linear low-density polyethylene (hereinafter also referred to as LLDPE) is mainly composed. In addition, the term "main component" herein means that the content is 50% by mass or more.

Such an LLDPE produced using a single activated site-based catalyst is excellent in adhesion to a cyclic polyolefin, and is reduced in adhesion even when exposed to high-temperature and high-humidity conditions by autoclaving. less. Therefore, the intermediate layer 12 having such an LLDPE as a main component is adjacent to the innermost layer 11 formed of the cyclic polyolefin, and the intermediate layer 12 can be transmitted through the intermediate layer 12. To follow the other layers further well and stably. Further, LLDPE produced by using a single activation site-based catalyst is also excellent in transparency, and has little deterioration even when exposed to high-temperature and high-humidity conditions. From this point of view, the multilayer body 10 having such an intermediate layer 12 is suitable for the formation of a medical container that needs to be sterilized by high pressure steam.

The LLDPE can be suitably used as long as it has a density of 0.860 g/cm ³ or more and 0.940 g/cm ³ which is produced by using a single activated site catalyst, but even if it is used, the density is 0.900~ 0.917 g/cm ³ can obtain a multilayer body 10 or a medical container which is more excellent in heat resistance, and does not cause any obstacle even when sterilized by high-pressure steam at 121 ° C, and the high-pressure steam is to be composed of a multilayer body. The reduction in peel strength between the intermediate layer 12 and the innermost layer 11 after sterilization of the medical container formed by 10 is suppressed. Here, when the density of the LLDPE is less than 0.860 g/cm ³ , the heat resistance is lowered. On the other hand, when the density of LLDPE is 0.940 g/cm ³ or more, the transparency or impact resistance of the container is lowered.

Further, in the LLDPE produced by a single activation site-based catalyst, it is preferable that the composition distribution of ethylene and α-olefin measured by the composition analysis is excellent in workability and impact resistance. For those who have such a characteristic, HARMONEX (registered trademark) manufactured by Nippon Polyethylene Co., Ltd., YUMERIT (registered trademark) manufactured by Ube Industries Co., Ltd., and EVOLU manufactured by PRIMEPOLYMER Co., Ltd. (registered trademark) can be used as appropriate. )Wait.

In addition, the intermediate layer 12 is made by a single activation site catalyst. The LLDPE to be produced is contained in an amount of 50% by mass or more, and is contained in an amount of 65% by mass or more, and more preferably 80% by mass or more from the viewpoint of flexibility. However, the adhesion to the innermost layer 11 is not inhibited. Within the scope, other polyethylene or cyclic polyolefins may also be included. In particular, when 30% by mass or less, more preferably 25% by mass or less, a high-density polyethylene having a higher density than LLDPE produced by a single activation site catalyst is used, heat resistance is improved by high pressure. The decrease in the adhesion of the steam-sterilized intermediate layer 12 is further suppressed. Further, when other polyethylene or cyclic polyolefin is used in combination with LLDPE as described above, there is an advantage that the multilayer body 10 excellent in appearance can be easily obtained.

Further, the intermediate layer 12 is also within the range of not impairing the effects of the present invention, and may contain, for example, a charge preventing agent, an oxidation preventing agent, a lubricant, an anti-fuzzing agent, an ultraviolet absorber, and a neutralizing agent within a usual range of use. Etc., various additives generally used in the field of resins.

The outermost layer 13 is formed as the outermost layer when the medical container is formed by the multilayer body 10, and is formed of high-density polyethylene (hereinafter also referred to as HDPE).

By providing the layer containing HDPE in the outermost layer 13, the heat resistance of the obtained multilayer body 10 is improved, and a medical container having less deterioration in characteristics such as surface deformation of the medical container by sterilization by high-pressure steam can be formed. In addition, in the case of the film-form multilayer body 10 of the example of Fig. 1, many of them are wound and stored in a roll shape, and the outermost layer 13 is provided with a layer containing HDPE, and the barrier property of the multilayer body 10 is also Excellent.

Although HDPE can be suitably used as long as it has a density of 0.940 to 0.970 g/cm ³ , in this case, if the density is 0.945 to 0.970 g/cm ³ , heat resistance and barrier resistance can be further improved. Multilayer body 10. Further, a plurality of HDPEs having different densities or the like may be used in combination.

Further, the suitable content of the HDPE in the outermost layer 13 varies depending on the density of the HDPE, for example, in the case of HDPE having a density of 0.945 to 0.970 g/cm ³ , such as 20% by mass or more in the outermost layer 13, It is possible to form a medical container which is less sterilized by high-pressure steam at 121 ° C and which has less deterioration in characteristics and has sufficient heat resistance. However, in order to achieve more stable heat resistance and barrier properties, the content of the HDPE of the outermost layer 13 is preferably 30% by mass or more, more preferably 70% by mass or more, and still more preferably 100% by mass.

However, in order to improve the forming stability, the outermost layer 13 may be used in combination with other resins. In this case, the content of the appropriate HDPE may be determined. The other resin may be a polyolefin of HDPE or higher, and a polyethylene resin such as a linear low-density polyethylene or a high-pressure low-density polyethylene may be suitably used. Among these, when the high-pressure method low-density polyethylene and HDPE are used together, the formation stability of the outermost layer 13 can be further improved. The high-pressure method low-density polyethylene is preferably one having a density of 0.910 to 0.935 g/cm ^{3 and} more preferably 0.920 to 0.935 g/cm ³ .

Further, the outermost layer 13 contains, within a normal range of use, a charge preventing agent, an oxidation preventing agent, a lubricant, an anti-fuzzing agent, an ultraviolet absorber, and a neutralizing agent, etc., insofar as the effects of the present invention are not impaired. Various additives generally used in the field of resins. In addition, the outermost layer 13 may also be denatured by bridging by electron beams or the like to improve heat resistance. By.

The total thickness of the multilayer body 10 is not particularly limited, but is usually 60 to 1000 μm. Considering the flexibility or strength of the multilayer body 10, it is preferably 100 to 600 μm, more preferably 100 to 400 μm.

The thickness of each layer is not particularly limited, and it is preferably 5 to 100 μm for the innermost layer 11 and 5 to 100 μm for the outermost layer 13. If the thickness of the innermost layer 11 is less than 5 μm, there is a possibility that the contained drug can be easily adsorbed, for example, more than 100 μm, the flexibility of the multilayer body 10, or the heat sealing when the medical container is formed from the multilayer body 10. There is a reduction in sex. Further, if the thickness of the outermost layer 13 is less than 5 μm, the heat resistance of the multilayer body 10 is lowered, and if it exceeds 100 μm, the transparency is lowered.

Therefore, in the case of the multilayer body 10 formed of three layers, the total thickness is set to 60 to 1000 μm, the innermost layer 11 is set to 5 to 100 μm, and the outermost layer is set to 5 to 100 μm. It is preferable to set it as the intermediate layer 12.

Further, when the multilayer body 10 formed of three layers is a thin film, the innermost layer 11 is set to 5 to 100 μm, the intermediate layer 12 is set to 50 to 300 μm, and the outermost layer is set to 5 to 100 μm. good.

As described above, the multilayer body 10 of the first embodiment is formed of three layers in which the innermost layer 11 made of a cyclic polyolefin and the outermost layer 13 including HDPE are satisfactorily joined via the intermediate layer 12, although In order to provide other characteristics of the multilayer body 10 for a medical container, for the purpose of further imparting other characteristics and the like, one or more layers may be provided between the intermediate layer 12 and the outermost layer 13 to form four or more layers. Such a layer can be mentioned: ethylene-ethylene a gas barrier resin layer such as an alcohol copolymer, an adhesive resin layer such as an ethylene-vinyl acetate copolymer, an ultraviolet shielding layer such as a polyolefin resin containing iron oxide, or the like, and benzodiazepine and adipate. A polyamine resin such as MXD nylon obtained from α, ω-plus-chain aliphatic dichloro acid, an oxygen absorbing layer formed of a cobalt salt, or the like.

Further, the shape of the multilayer body is not limited to the multilayer body 10 formed as a film as shown in Fig. 1, and as described later in detail, it may be formed by blowing by a multilayer blow molding method (multilayer hollow molding method). A multilayer body having a three-dimensional shape such as a body.

The medical container according to the present invention is a medical container including a housing portion for storing a chemical liquid, and at least the housing portion is formed of the above-described multilayer body. At that time, the innermost layer becomes the inner side of the accommodating portion, and the outermost layer is disposed outside. Further, in the medical container, a mouth portion which is an injection flow outlet for the chemical liquid is formed outside the housing portion.

Hereinafter, specific examples of the medical container of the present invention will be described in detail using the drawings.

The second drawing is a medical container 20 in which the accommodating portion 21 and the gargle portion 22 are integrally formed by a multi-layer blow molding method. The upper portion of the medical container 20 is a hanging portion 23 in which a hanging hole is formed, and the lower mouth portion 22 is attached to the outer peripheral portion of the side surface of the cylindrical rubber material that can pierce the injection needle by injection molding. The rubber plug 22a of synthetic resin which can be welded to the innermost layer 11 is provided and sealed.

This medical container 20 can be manufactured by a conventional multi-layer blow molding method using a multi-layer blow molding machine. Coming out the multilayer parison and using the mold After the multilayer parison is sandwiched, the clean air may be blown into the multilayer parison. In the mold here, the medical container 20 of Fig. 2 formed of a hollow blow-molded body can be formed by using the accommodating portion 21 and the mouth portion 22 integrally. In addition, when the multi-layer parison is twisted by the mold, the air is blown in advance with clean air, and after the mold is closed, the vacuum is formed in the mold to make the inside of the mold a negative pressure, so that the transfer precision of the mold can be made. improve.

In addition, the method of forming the mouth portion is formed by integrating the forming method with the accommodating portion by a plurality of layers, and for example, a circle prepared separately as in the example of Fig. 3 to be described later A method in which the tubular member is heat-sealed to the accommodating portion, or a method in which the cylindrical member is embedded and blown into shape and integrated simultaneously with the forming. Further, in the case where the cylindrical member is used, the cylindrical member may be sealed by the rubber plug 22a, and may be used in detail as shown in the third (B). After the rubber plug is loaded into the cylindrical member, the peripheral portion of the rubber plug is pressed by the annular cover member, and the cover member is welded to the cylindrical member by ultrasonic waves or the like to seal the shape.

Fig. 3(A) is a view showing a housing portion 31 formed by hot plate forming of a film, and a mouth portion formed of a cylindrical member and sealed by heat sealing of the rubber plug 32a. 32 medical containers 30. The accommodating portion 31 of the medical container 30 is formed by laminating two sheets of the film-formed product 10' of Fig. 4, and the peripheral portion 33 is heat-sealed.

That is, in the case of manufacturing the medical container 30, first, a film-like multilayer in Fig. 1 is formed by hot plate forming such as vacuum forming or pressure forming. The central portion of the body 10 is formed with a concave portion along the inner shape of the accommodating portion 31 to obtain the film-formed product 10' shown in Fig. 4. Next, two of the film molded articles 10' are prepared, and the concave portions are superposed in a direction in which the concave portions face each other. Further, the cylindrical member is placed at a specific position, and the peripheral portion of the film-formed product 10' is entangled to be heat-sealed. The heat sealing temperature differs depending on the total thickness of the multilayer body 10, and is not particularly limited, and is preferably about 150 to 280 °C. In addition, after heat sealing, the peripheral portion may be trimmed as needed. According to this method, the medical container 30 of the third (A) diagram can be manufactured by simultaneously forming the accommodating portion 31 and the formation of the mouth portion 32 by heat sealing of the cylindrical member.

Further, the formation of the accommodating portion 31 and the formation of the mouth portion 32 may be performed by another project.

The material of the cylindrical member forming the mouth portion 32 is preferably a cyclic polyolefin as in the innermost layer 11 of the multilayer body 10, based on the relationship with the heat sealability of the accommodating portion 31. However, as long as it is The accommodating portion 31 can be heat-sealed in a liquid-tight manner, and is not limited to a cyclic polyolefin. LLDPE produced by a single activation site-based catalyst, a composition similar to the intermediate layer 12, or the like can be used. Further, a resin which can be heat-sealed may be used for a plurality of layers of the heat sealing surface of the cylindrical member. Further, instead of being formed of the cylindrical member and the rubber plug 32a, as shown in Fig. 3(B), after the rubber stopper 32b is loaded into the cylindrical member, the rubber stopper 32b is pressed by the annular cover member 32c. In the peripheral portion, the cover member 32c and the cylindrical member are welded by ultrasonic waves or the like to form the mouth portion 32 here.

Fig. 5 is a view showing the formation of a film-like multilayer body 10 as shown in Fig. 1 The bag-shaped accommodating portion 41; and the so-called film bag type medical container 40 of the crotch portion 42 formed of a cylindrical member.

In the medical container 40 of this example, a multi-layered body formed into a tubular shape by a multi-layer inflation method or the like is used, and the accommodating portion 41 is not formed at both ends thereof by heat sealing, and the cylindrical member is heat-sealed at a specific position at one end thereof. The mouth portion 42 is manufactured by forming a hanging portion at the other end. The heat sealing at both ends and the heat sealing of the cylindrical member may be performed simultaneously or separately. Further, instead of using a cylindrical multilayer body, it is also possible to use two multilayer bodies 10 as shown in Fig. 1, and after laminating them, the accommodating portion is formed by heat-sealing the peripheral portion.

Further, in this example, the mouth portion 42 is a cylindrical member formed of LLDPE or the like which is made of a cyclic polyolefin or a single activation site catalyst; and a rubber plug 42a which can pierce the injection needle; The annular cover member 42b of the peripheral portion of the rubber plug 42a is sealed.

According to the medical container described above, at least the accommodating portion is provided with: an innermost layer formed of a cyclic polyolefin; and a linear low-density polyethylene produced by using a single activated site-based catalyst as a main component An intermediate layer; and a multilayered body containing the outermost layer of high-density polyethylene, each layer can be well adhered to, has hygienic properties, and is excellent in heat resistance, and in the case of autoclaving, properties such as transparency and peel strength are deteriorated. less.

Further, the shape of the medical container is not limited to a configuration including one accommodating portion. For example, as shown in Fig. 6, the accommodating portion 51 may be partitioned by the partition wall sealing portion 52 that can communicate with each other. The plurality of medical treatment containers 50 capable of individually accommodating a plurality of kinds of chemical liquids are plural.

In the medical laboratory container 50 of the sixth embodiment, the partition sealing portion 52 is provided along the width direction of the accommodating portion 51 formed in a bag shape, and the accommodating portion 51 is divided into the first accommodating portion 51a and the second accommodating portion 51b. When the partition sealing portion 52 is used in the case medical container 50, the user peels off the first housing portion 51a or the second housing portion 51b from the outside, and the chemical solution in the first housing portion 51a is second. The chemical liquid in the accommodating portion 51b is mixed.

The method of forming the partition sealing portion 52 is not limited. For example, when the accommodating portion 51 is formed, when it is heat-sealed, it may be formed by heat sealing. Further, in addition to the heat sealing, it may be carried out separately by a known sealing method such as pulse sealing. Further, in the case where the accommodating portion 51 is manufactured by blow molding, the mold used for forming the partition wall sealing portion 52 may be provided in a mold used for blow molding to form a partition wall while being blow molded. Sealing portion 52.

Further, although not shown in the drawings, the medical container of the present invention may be provided with a light shielding layer for protecting the chemical liquid on the outside, particularly on the outer side of the accommodating portion. The material suitable for the light-shielding layer may, for example, be a metal foil such as aluminum foil, an aluminum vapor-deposited film, a laminated film of a metal foil and a synthetic resin film, or a synthetic resin film containing a pigment. Among these light-shielding layers, aluminum foil, aluminum vapor-deposited film, and the like are not only light-shielding, but also have moisture-proof property, oil resistance, non-absorbability, etc., and are improved from the viewpoint of improving the long-term storage property of the chemical solution contained in the medical container. In terms of, it is more appropriate. Alternatively, the light shielding layer may be provided to be detachable from the medical container, and when used in a medical container, the medical solution may be visually observed from the outside.

As described above, the medicine is contained in the medical container of the present invention. The liquid is described as an example, but it may be not only a chemical liquid but also a drug formed of a powder such as an antibiotic substance. Further, specific examples of the chemical solution include a physiological saline solution, a circulator system drug, a contrast agent, and an antibacterial agent, which are used as an injection. However, it is not limited to these.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[Example 1]

The medical container 20 of Fig. 2 filled with 100 ml of water was produced as follows.

First, by using a multilayer blow molding method using a multi-layer blow molding machine, 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 integrally formed in this order. The accommodating portion 21 and the mouth portion 22 formed by blowing the body of the layer structure. Next, the container portion 21 is filled with water 100 ml from the mouth portion 22, and then the rubber plug 22a is heat-sealed to the mouth portion 22 to seal the medical container 20. The rubber plug body 22a is provided on the outer peripheral portion of the rubber plug by an injection molding method in accordance with the melt flow rate in 280 ° C according to ISO 1133 (hereinafter referred to as [MFR]. In addition, in the examples and the comparative examples, In the MFR measurement, all of the load is 21.18 N.) The cyclic polyolefin "ZEONEX (manufactured by Nippon Zeon Co., Ltd.)" having a glass transition temperature of 136 ° C (hereinafter referred to as "COP1"). The layer formed.

In addition, the innermost layer is a cyclic polyolefin "ZEONOA (manufactured by Nippon Zeon Co., Ltd.)) which has COP1 and an ISO 1133, an MFR of 280 ° C of 20 g/10 min, and a glass transition temperature of 102 ° C (hereinafter) It is called "COP2".) A mixture of cyclic polyolefins mixed in a mass ratio of 1:1. The Tg of this mixed cyclic polyolefin was only observed at 119 °C.

For the intermediate layer, LLDPE (hereinafter, also referred to as a single activation site system LLDPE) which is produced by a single activation site-based catalyst, and HDPE having a MFR of 1 g/10 min and a density of 0.906 g/cm ³ at 190 ° C are used. "HARMOREX (made by Nippon Polyethylene Co., Ltd.)" and HDPE "NOVATEC (made by Nippon Polyethylene Co., Ltd.) having an MFR of 3.5 g/10 min and a density of 0.956 g/cm ³ at 190 ° C with a quality of 8:2 Better than being mixed.

In the outermost layer, HDPE "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" having an MFR of 3.5 g/10 min and a density of 0.955 g/cm ³ at 190 ° C was used.

The medical container 20 obtained in Fig. 2 filled with water thus obtained was subjected to autoclaving at 121 ° C for 30 minutes by spray-type autoclaving, and the characteristics before and after the evaluation were evaluated as follows. in.

Further, in the examples and the comparative examples, the evaluation of the barrier property and the forming stability was carried out only in the case of forming a film and forming an accommodating portion, and as in the case of Example 1, it was formed by multi-layer blow molding. In the case of the accommodating department, no evaluation is made.

(evaluation method)

(1) Barrier resistance Two multilayered bodies of 10 cm × 10 cm were laminated so that the outermost layers thereof were in contact with each other, and a load of 98 N/100 cm ² was applied thereto, and kept at 60 ° C for 24 hours. Thereafter, the mixture was cooled to room temperature, and after removing the load, the two films were peeled off. The peeling state at this time was evaluated in the following two stages.

○: Easy to peel off ×: There is resistance when peeling off

(2) Peel strength A rectangular sample S having a width of 15 mm was cut out from the medical container before and after autoclaving, and is schematically shown in Fig. 7(A), and the innermost layer 11 and the intermediate layer 12 were measured at a tensile speed of 300 mm/min. It is based on the T-shaped peel strength of JIS K6854-3. The test was carried out by means of a tensile tester. The symbol P in the figure indicates the chuck of the tensile tester.

Further, as shown in Fig. 7(A), the sample S is formed such that only the innermost layer 11 is broken at the breaking portion V, first, as shown in the plan view of Fig. 7(B). The both ends of the sample S cut out from the medical container in the width direction are provided with the cut marks C at two positions facing each other, and the sample S is oriented in the longitudinal direction as indicated by the arrow in the seventh (B) diagram. Stretching. In this way, the portion of the incision C can be obtained, and only the innermost layer 11 is completely broken, and the other layers are not broken. Therefore, by setting it up The tensile strength of the interface between the innermost layer 11 and the intermediate layer 12 can be measured by placing it in a tensile tester as shown in Fig. 7(A).

(3) Transparency The haze before and after autoclaving was measured in accordance with JIS K 7136.

(4) Heat resistance The medical container placed on the punched metal tray with the round hole was autoclaved by a spray type autoclave to visually evaluate the appearance of the medical container.

○: No deformation or shrinkage after sterilization.

△: The surface is rough, etc., and there is a slight deformation and contraction.

×: Large deformation or shrinkage, and there are round-hole tray marks and the like.

(5) Forming stability The shape stability of the tube-shaped film in the inflation molding and the occurrence of collapse of the film were evaluated.

○: The tube shape is constant. No creases were seen in the film.

×: The tube shape is unstable and the tube diameter is deviated. The pleats were seen in the film portion.

[Embodiment 2]

In the first embodiment, the medical container 20 is obtained except that the composition of the outermost layer and the configuration of the mouth portion 22 are changed.

The outermost layer is a high-pressure method low-density polyethylene "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" having an MFR of 190 C of 1.1 g/10 min and a density of 0.927 g/cm ³ ; and an MFR of 3.5 g at 190 ° C. The high-density polyethylene "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" having a density of 0.956 g/cm ^{3 in} /10 minutes was mixed at a mass ratio of 7:3.

The mouth portion 22 is a cylindrical member formed of a cyclic polyolefin produced by injection molding, heated by a preheating mold set at 250 ° C, and inserted into a container formed by the blow molded body of Fig. 2 The side of the mouth portion 22 of the portion 21 is heat sealed by 220C and attached. In addition, after filling 100 mL of water, the rubber plug was placed in the cylindrical member, and then the annular cover member was pressed against the peripheral edge portion of the rubber plug, and the cylindrical member and the cover member were ultrasonically welded. Further, COP1 is used for the cylindrical member and the lid member. Further, it was evaluated in the same manner as in Example 1. The results are shown in the table.

[Example 3]

In the formation of the innermost layer, the medical container 20 was obtained in the same manner as in the first embodiment except that COP2 was used, and the evaluation was performed in the same manner. The results are shown in the table.

Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug to provide a layer formed of LLDPE used in the intermediate layer by injection molding.

[Example 4]

In the formation of the intermediate layer, a single activation site of LLDPE "HARMOREX (manufactured by Nippon Polyethylene Co., Ltd.)" having a MFR of 3.5 g/10 min and a density of 0.918 g/cm ³ at 190 ° C was used. In the same manner as in Example 3, the medical container 20 was obtained and evaluated in the same manner. The results are shown in the table.

Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug to provide a layer formed of LLDPE used in the intermediate layer by injection molding.

[Example 5]

In the formation of the intermediate layer, a single activation site of LLDPE "YUMERIT (manufactured by Ube Industries Co., Ltd.)" having an MFR of 4.0 g/10 min and a density of 0.931 g/cm ³ at 190 ° C was used. In the same manner, the medical container 20 was obtained and evaluated in the same manner. The results are shown in the table.

Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug to provide a layer formed of LLDPE used in the intermediate layer by injection molding.

[Embodiment 6]

For the formation of the intermediate layer, a single activation site of LLDPE "YUMERIT0520F (manufactured by Ube Industries, Ltd.)" having an MFR of 190 ° C of 2.0 g/10 min and a density of 0.904 g/cm ³ was used; and 190 ° C was used. The medical container 20 was obtained in the same manner as in the first embodiment except that HDPE "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.) having a MFR of 3.5 g/10 min and a density of 0.956 g/cm ³ was mixed at a mass ratio of 8:2. , the same assessment. The results are shown in the table.

Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug to provide a layer formed of COP1 by injection molding.

[Embodiment 7]

The medical container 30 of Fig. 3 filled with 100 ml of water was produced as follows.

First, an inner layer having a thickness of 10 μm, an intermediate layer having a thickness of 220 μm, and an outer layer having a thickness of 20 μm are sequentially formed by laminating three layers by a multilayer inflation method using a multi-layered air-filled film forming machine. Inflatable film.

Then, the film sheet obtained by cutting the gas-filled film was softened by radiant heating by a heater set at 300 ° C, and molded by a vacuum forming machine using a mold at normal temperature to obtain a film-formed product of FIG. 10'.

Then, the film molded article 10' is laminated in such a manner that the concave portions face each other, and the peripheral portion is heat-sealed, and then the cylindrical member of the injection molded article of the cyclic polyolefin is heat-sealed to form a gargle. Part 32.

Then, 100 ml of water is filled in the accommodating portion 31 from the mouth portion 32, and as shown in Fig. 3(B), the rubber stopper 32b is loaded into the cylindrical member, and then the annular cover member 32c is pressed. For rubber pin 32b The peripheral portion is disposed to ultrasonically weld the cylindrical member and the lid member 32c. Further, COP1 is used for the cylindrical member and the lid member 32c.

Further, the same resin as in Example 1 was used for the innermost layer, the intermediate layer, and the outermost layer.

The evaluation of the sealed medical container 30 is then performed. The results are shown in the table.

[Embodiment 8]

The medical container 40 of Fig. 5 filled with 100 ml of water was produced as follows.

First, in the same manner as in Example 7, an air-filled film having a three-layer structure was produced.

Then, both end portions of the gas-filled film are heat-sealed to form a bag shape, and a cylindrical member of the injection molded article of COP 2 is heat-sealed at one end thereof, and a mouth portion 42 is formed in the film bag-type accommodating portion 41.

After the water is filled in the accommodating portion 41 from the mouth portion 42, the rubber plug 42b is loaded into the cylindrical member, and then the annular cover member 42b is pressed against the peripheral edge portion of the rubber plug 42a. The cylindrical member and the cover member 42b are ultrasonically welded. Further, COP1 is used for the cylindrical member and the lid member 42b.

Evaluation is then performed on the sealed medical container 40. The results are shown in the table.

[Embodiment 9]

In the outermost layer, a high-pressure method low-density polyethylene "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" having a MFR of 1 g/10 min and a density of 0.927 g/cm ³ at 190 ° C was used; and the MFR at 190 ° C was 3.5. The medical container 20 was obtained in the same manner as in the eighth embodiment except that the high-density polyethylene having a density of 0.956 g/cm ³ and a density of 0.956 g/cm ³ was mixed at a mass ratio of 7:3. The assessment is performed in the same way. The results are shown in the table.

[Embodiment 10]

In addition to the outermost layer, a linear low-density polyethylene manufactured by Ziegler catalyst having an MFR of 190 C of 2.0 g/10 min and a density of 0.936 g/cm ³ was used. And the high-density polyethylene having a MFR of 3.5 g/10 min and a density of 0.956 g/cm ³ at 190 ° C, "NOVATEC (made by Nippon Polyethylene Co., Ltd.)" is mixed in a mass ratio of 7:3. The medical container 20 was obtained in the same manner as in Example 8 except that the evaluation was performed 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, instead of a single activation site type LLDPE, a ZFRler catalyst was used using an MFR at 190 ° C of 1.1 g/10 min and a density of 0.906 g/cm ³ . The formation and evaluation of the medical container were carried out in the same manner as in Example 1 except for LLDPE (manufactured by Nippon Polyethylene Co., Ltd.). The evaluation results are shown in the table.

[Comparative Example 2]

In the formation of the intermediate layer, LLDPE (MOATEC (manufactured by PRIME POLYMER Co., Ltd.) manufactured by Ziegler Catalyst) having a MFR of 190 ° C of 2.0 g/10 min and a density of 0.920 g/cm ³ was used. The formation and evaluation of the medical container were carried out in the same manner as in Example 1. The evaluation results are shown in the table.

[Comparative Example 3]

The formation and evaluation of the medical container were carried out in the same manner as in Example 1 except that the outermost layer and the two layers of the innermost layer and the intermediate layer were not formed. The evaluation results are shown in the table.

[Comparative Example 4]

In the formation of the outermost layer, instead of HDPE, LLDPE "MOATEC (PRIME Co., Ltd.) manufactured using Ziegler catalyst using MFR of 190 ° C of 2.0 g/10 min and density of 0.920 g/cm ³ was used. The formation and evaluation of the medical container were carried out in the same manner as in Example 1 except for the production of POLYMER. The evaluation results are shown in the table.

[Comparative Example 5]

In the formation of the outermost layer, in place of HDPE, the MFR at 190 ° C is 2.0 g/10 min, and the density is 0.920 g/cm ³ . LLDPE manufactured by Ziegler Catalyst (MOATEC (manufactured by PRIME POLYMER Co., Ltd.) The formation and evaluation of the medical container were carried out in the same manner as in Example 8. The evaluation results are shown in the table.

In the examples 1 to 3 and 6 to 10 in which the single active site is used as the main component of the intermediate layer and the HDPE is used in combination, the reduction in peel strength or transparency by autoclaving can be suppressed, and heat resistance is suppressed. Also excellent medical container. On the other hand, in the medical container obtained in Comparative Example 1 in which the 戚German LLDPE and the HDPE were used together, the peel strength or the transparency of the autoclave was greatly reduced. The comparison of the intermediate layer was carried out only in Examples 3 and 5 in which a single activation site was LLDPE and Comparative Example 2 in which only the Ragler-type LLDPE was used, and the same tendency was observed.

In Comparative Example 3 in which the outermost layer was not provided, the transparency of autoclaving was greatly reduced, 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 also observed. As the outermost layer component, in Examples 9 and 10 in which HDPE was used together with high-pressure method low-density polyethylene, the molding stability was further improved as compared with Example 7 or 8 in which the outermost layer was only HDPE.

Further, in Example 8, although the film was excellent in barrier resistance, it was poor in Comparative Example 5.

[Industry use possibility]

According to the present invention, it is possible to provide a medical treatment in which the innermost layer and the other layer formed of the cyclic polyolefin can be satisfactorily adhered without using an adhesive, and the heat resistance is also excellent, and in the case of a film, the barrier property is also good. A multi-layered container for containers; and a medical container formed of a multilayered body of the medical container, which is sterilized by high-pressure steam or the like, and which has little deterioration in characteristics such as transparency and peel strength. Therefore, the present invention is industrially useful.

10‧‧‧Multilayer

11‧‧‧ innermost layer

12‧‧‧Intermediate

13‧‧‧outer Floor

20, 30, 40‧ ‧ medical containers

50‧‧‧Re-hospital medical container

Fig. 1 is a cross-sectional view showing an example of a multilayer body of the present invention.

Fig. 2(A) is a plan view showing an example of the medical container of the present invention, and Fig. 2(B) is a cross-sectional view taken along line I-I' of (A).

Fig. 3(A) is a plan view showing another example of the medical container of the present invention. (B) is a plan view showing another example of the mouth part.

Fig. 4(A) is a front view showing a film molded article used in the production of the medical container of Fig. 3, and Fig. 4(B) is a side view thereof.

Fig. 5 is a plan view showing still another example of the medical container of the present invention.

Fig. 6 is a plan view showing a medical laboratory container of an example of the medical container of the present invention.

Figure 7(A) is a model diagram illustrating the peel test of the embodiment, (B) is a plan view showing the method of producing the sample used in (A).

10‧‧‧Multilayer

11‧‧‧ innermost layer

12‧‧‧Intermediate

13‧‧‧ outermost layer

Claims (6)

A multilayer body for a medical container, which is a multilayer body for a medical container formed by forming a medical container, characterized by: an innermost layer formed of a cyclic polyolefin; and an adjacent innermost layer formed by A linear low-density polyethylene having a density of 0.900 g/cm ³ to 0.917 g/cm ³ manufactured using a single-site catalyst, and further containing an intermediate layer of high-density polyethylene And the outermost layer containing high-density polyethylene, and manufactured by multi-layer blow molding or multi-layer inflation. The multilayered body for a medical container according to the first aspect of the invention, wherein the cyclic polyolefin is a hydrogen additive of a ring-opening polymer of a cyclic olefin monomer. The multilayer body for a medical container according to the first aspect of the invention, wherein the outermost layer is a mixture of the high-density polyethylene and the high-pressure method low-density polyethylene. The multilayer body for a medical container according to the first aspect of the invention, wherein the outermost layer is formed only of the high-density polyethylene. A medical container comprising a medical container for accommodating a medical solution, wherein at least the accommodating portion is formed of a multilayer body for a medical container according to the first aspect of the invention. The medical container according to claim 5, wherein the multilayer body for the medical container is blown into a shape or a film, and when the multilayer body for the medical container is a film, the accommodating portion heats the film. Forming the sheet; or forming the aforementioned film into a bag shape.