JP3227709B2 - Medical or food packaging containers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical or food packaging container, and more particularly, to a change in the content of a content which is impermeable to water and which is eluted from the material of the content or a material eluted from the material of the container. Relates to a multi-layer container having a small size. In addition, the present invention relates to a multilayer container which does not allow moisture to permeate and is excellent in gas barrier properties and has little change in composition and deterioration of contents. Further, the present invention relates to a container having good transparency and capable of detecting contents by an optical method from the outside of the container. Furthermore, the book
The invention relates to multilayer containers such as medical containers and food packaging containers.
It relates to a suitable multilayer film or sheet.

[0002]

2. Description of the Related Art Polymer materials used for medical containers such as infusion bags, blood bags, drug bottles, analytical cells, and medical test tubes are mainly made of polyvinyl chloride, polyethylene, polypropylene, polystyrene, and the like.
ABS resin and the like. These medical containers are required to have transparency, chemical resistance, impact resistance, repeatable sterilization, and the like.Conventional containers made of a polymer material, for example, become white due to water absorption when steam sterilized, and become transparent. Loss, heat resistance and chemical resistance are not sufficient, water vapor permeability and gas permeability are large, plasticizers and trace impurities are eluted, and elution and moisture permeation are not possible such as polyethylene and polypropylene. Each has problems, such as those that are small but opaque and have insufficient heat resistance.

[0003] Above all, those having moisture permeability, gas permeability or elution of a plasticizer or trace impurities cause a change in the composition or alteration of the contents contained in the container. In addition, medical containers are required to be able to visually check the contents of liquid medicines and body fluids from the outside, and high transparency is a great advantage. In particular, a medical container for detecting the content, composition, color, etc. of the contents by an optical method is inappropriate if the container has insufficient transparency. On the other hand, in a food packaging container such as miso, soy sauce, mayonnaise, etc., if it has water vapor permeability, it causes a decrease in taste and deterioration of food.

Conventionally, various medical or food packaging containers having improved transparency and gas barrier properties using a polymer material have been developed, but they are impermeable to water, heat resistant, and steam resistant. It is still insufficient in terms of sterility and the like. In particular, along with transparency, gas barrier properties, chemical resistance, etc.
Medical or food packaging containers having excellent properties such as moisture impermeability, heat resistance, and steam sterilization resistance have not yet been proposed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a medical or food packaging container which has excellent resistance to water vapor transmission and has no change in composition such as the water content of the contents. Another object of the present invention is to provide a container having water impermeability and gas impermeability. Another object of the present invention is to provide a container having excellent moisture impermeability, good transparency, no cloudiness due to water absorption whitening, and capable of detecting the components, composition, color, etc. of the contents by an optical method. Is to provide. The inventors of the present invention have conducted intensive studies to overcome the problems of the prior art, and as a result, it has been found that a multilayer container of two or more layers made of different materials using various synthetic resins or aluminum foils, and at least one layer thereof is provided. By using a thermoplastic saturated norbornene-based polymer layer, it has been found that a container with significantly improved water vapor transmission resistance can be obtained.

Further, by forming a multilayer including a thermoplastic saturated norbornene-based polymer layer and a gas barrier resin layer, a container having water vapor transmission resistance and gas barrier properties can be obtained. Further, by combining with a transparent resin layer and / or a transparent gas barrier resin layer, a container having water impermeability and excellent transparency can be obtained. Further, by using the thermoplastic saturated norbornene-based polymer layer as the innermost layer, a container free from cloudiness due to water absorption whitening during steam sterilization can be obtained. The present invention has been completed based on these findings.

[0007]

Thus, according to the present invention, there is provided a container comprising a multilayer having at least two layers having different wall materials, wherein at least one of the layers has a thermoplastic saturated norbornene-based polymer layer. der is, and thermoplastic
Saturated norbornene-based polymer contains polar monomer
Of a norbornene monomer having a ratio of 30 mol% or less
Hydrogenated ring-opening polymer, the norbornene-based monomer and
Copolymer with ethylene and hydrogenated product of the copolymer
Medical or food packaging container according to claim et saturated polymer der Rukoto selected is provided. Further, according to the present invention, a multilayer film or sheet comprising a that at least two layers of different materials, Ri least one layer thermoplastic saturated norbornene-based polymer layer der of them, and, thermoplastic
Saturated norbornene-based polymer contains polar monomer
Of a norbornene monomer having a ratio of 30 mol% or less
Hydrogenated ring-opening polymer, the norbornene-based monomer and
Copolymer with ethylene and hydrogenated product of the copolymer
Et multilayer film or sheet Ru saturated polymer der selected is provided. Hereinafter, the present invention will be described in detail.

(Thermoplastic saturated norbornene-based polymer)
Specific examples of the thermoplastic saturated norbornene-based polymer used in the present invention include a polymer having a structural unit represented by the following Chemical Formula 1 and / or Chemical Formula 2.

[0009]

Embedded image (Wherein, R ₁ and R ₂ are hydrogen or carbon 1
10 to 10 hydrocarbon residues, which may be the same or different, and R ₁ and R ₂ may form a ring with each other. n is a positive integer. )

[0010]

Embedded image (Wherein, R ₃ and R ₄ are hydrogen or carbon 1
And the same or different hydrocarbon residues, and R ₃ and R ₄ may form a ring with each other. l and m are positive integers, and p is 0 or a positive integer. )

The polymer having a structural unit represented by the following chemical formula (I) is used as a monomer, for example, norbornene and its alkyl and / or alkylidene-substituted product, for example,
5-methyl-2-norbornene, 5,6-dimethyl-2
-Norbornene, 5-ethyl-2-norbornene, 5-
Butyl-2-norbornene, 5-ethylidene-2-norbornene and the like; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, and alkyl substituted products thereof such as methyl, ethyl, propyl and butyl; dimethanooctahydronaphthalene; And its alkyl and / or alkylidene substituents, for example, 6-methyl-1,
4: 5,8-Dimethano-1,4,4a, 5,6,7,
8,8a-octahydronaphthalene, 6-ethyl-1,
4: 5,8-Dimethano-1,4,4a, 5,6,7,
8,8a-octahydronaphthalene, 6-ethylidene-
1,4: 5,8-dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene and the like; cyclopentadiene trimer to tetramer, for example, 4,9: 5,8-dimethano-3a, 4,4a, 5,8,8a, 9,9a-octahydro- 1H-benzoindene, 5,8-methano-3
a, 4,4a, 5,8,8a, 9,9a-octahydro-1H-benzoindene, 5,8-methano-1,4,4
a, 4b, 5,8,8a, 9b-octahydro-1H-
Fluorene, 4,11: 5,10: 6,9-trimethano-3a, 4,4a, 5,5a, 6,9,9a, 10,1
Saturation produced by subjecting a ring-opened polymer obtained by polymerizing by a known ring-opening polymerization method using 0a, 11,11a-dodecahydro-1H-cyclopentaanthracene or the like to hydrogenation by an ordinary hydrogenation method. It is a polymer. Further, the polymer having the structural unit represented by Chemical Formula 2 is a polymer obtained by copolymerizing a norbornene-based monomer as described above and ethylene by a known method, and / or
Or a hydrogenated product thereof, each of which is a saturated polymer.

For the purpose of the present invention, the above-mentioned thermoplastic saturated norbornene-based polymer comprising only a monomer containing no polar group is preferable from the viewpoint of water impermeability. It may be a polymer obtained by copolymerizing a partially polar monomer. In this case, examples of the polar monomer include a substituent obtained by introducing a halogen group such as chlorine or bromine or an ester group into the above-described norbornene-based monomers. However, as the ratio of copolymerization of these polar monomers becomes higher, the resulting polymer becomes more likely to absorb water or more easily permeate water. The ratio is preferably 30% or less in molar ratio.

From the viewpoint of heat resistance, these polymers have a glass transition temperature of preferably 100 ° C. or higher, more preferably 120 ° C. to 200 ° C., and particularly preferably 130 ° C. to 1 ° C.
80 ° C. As for the molecular weight range, the number average molecular weight measured by GPC (gel permeation chromatography) analysis using toluene as a solvent is from 100,000 to 100,000, preferably from 20 to 70,000. If it is less than 10,000, strength will be insufficient, and if it exceeds 100,000, workability will be poor. When the carbon-carbon unsaturated bond remaining in the molecular chain is saturated by hydrogenation, the hydrogenation rate is 90% or more.
It is preferably at least 95%, particularly preferably at least 99%. By being a saturated polymer, weather resistance, light resistance, and the like are improved. Further, the thermoplastic saturated norbornene-based polymer may be used in the course of producing a polymer having the structural units represented by Chemical Formula 1 and Chemical Formula 2 within a range that does not impair the object of the present invention. A monomer component may be copolymerized.

In order to be able to observe, inspect, or detect an internal object from the outside, the light transmittance of the laminate must be 70% or more over visible light or over the entire region (wavelength 400 to 700 nm). In a typical inspection, light in the near-ultraviolet region is frequently used, and light having a shorter wavelength is more likely to be absorbed by the polymer. Therefore, the light transmittance at a wavelength of 400 nm particularly affects the performance of the polymer. The thermoplastic saturated norbornene-based polymer layer has low light absorption even at a wavelength of 400 nm, and can have excellent transparency with a light transmittance of 85% or more, preferably 90% or more when measured by a single layer. . Here, the light transmittance is a value measured with a spectrophotometer against air.

In order to prevent the composition change and deterioration of the contents,
It is better that the material of the container does not absorb or transmit moisture as much as possible. In this respect, thermoplastic saturated norbornene polymers are moisture absorption (JIS K-6911 compliant) is 0.01% or less, moisture permeability even 1mm thickness at 0.01 g / m ²
-24 hr (water vapor permeability tester manufactured by Shibata Chemical Co., Ltd., the moisture permeating the plate is measured by a change in the weight of the hygroscopic agent), which is very small (1/100 or less of PC and PMMA), and is a suitable material. Until now, heat resistance of 100 ° C or more (heat deformation temperature)
There was no polymer having low moisture absorption and water impermeability. The thermoplastic saturated norbornene-based polymer used in the present invention has not only heat resistance, but also excellent chemical resistance, moisture absorption resistance, water vapor transmission resistance, etc., or loses transparency during sterilization or storage, or Changing the water content of the stored contents is suppressed.

The thermoplastic saturated norbornene-based polymer itself has excellent characteristics as an optical material including a lens material, as disclosed in JP-A-60-26024, JP-A-64-24826, and JP-A-64-24826. 60-168708
JP, JP-A-61-115912, JP-A-61-159912
It is a known polymer material disclosed in JP-A-120816 and the like. However, it has not been proposed to use this thermoplastic saturated norbornene-based polymer to form a composite container with another resin material or the like to form a multilayer container.

[0017] (gas barrier resin) primarily oxygen, such a problem Runode as gas causing deterioration or change in composition of the contents, the oxygen transmission rate may ^{smaller, 1cc / m 2 · 24hr ·} atm or less And preferably 0.5 cc / m ^2.
24 hr · atm or less, more preferably 0.3 cc /
m ² · 24 hr · atm or less. The thermoplastic saturated norbornene-based polymer itself has a moderate gas barrier property, for example, about 1 cc / m ² .multidot.
It has a gas barrier property of 24 hr · atm, and this value largely depends on the thickness. A particularly preferred multilayer container of the present invention can impart more preferable gas barrier properties together with water vapor permeability resistance by including another resin layer having excellent gas barrier properties.

As the gas barrier resin, general-purpose resins in the field of packaging materials and the like can be used. A preferred method of use is to use a resin having a better gas barrier property than a thermoplastic saturated norbornene-based polymer at an appropriate thickness,
0.5 cc / m ² · 24 hr · atm at oxygen permeation rate
The following layers should be selected and used, otherwise, the composite does not improve the gas barrier properties as a laminate. For example, ethylene-vinyl alcohol copolymer (EVOH), vinylidene chloride-based polymer (PVD
C), barrier polyesters such as polyethylene-isophthalate copolymer, MXD6 nylon (m-xylylene adibamide), barrier nylon (amorphous nylon), polyacrylonitrile, liquid crystal polyester,
Whole aromatic nylon (aramid), polyvinyl acetate or its hydrolyzate (PVA), etc. are mentioned as effective examples. Further, transparent multilayer films such as PVDC-coated biaxially-stretched polyethylene terephthalate, PVDC-coated biaxially-stretched polypropylene, and PVDC-coated biaxially-stretched polyvinyl alcohol may also be used.

(Other Layers) The multilayer container of the present invention comprises a gas barrier resin layer instead of a gas barrier resin layer.
Alternatively, the thermoplastic saturated norbornene-based polymer layer alone may include other layers together with the gas barrier resin layer in order to compensate for insufficient bending strength, bending resistance , and tensile strength. As a resin material constituting other layers,
There is no particular limitation as long as it is a resin material used for medical or food packaging. For example, polyethylene terephthalate (PET), polybutylene terephthalate (P
BT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ionomer resin, polystyrene (PS), ABS resin, Various synthetic resins such as thermoplastic elastomer, nylon (polyamide resin), ethylene-vinyl acetate copolymer (EVA), polymethylpentene, and polysulfone can be exemplified. These synthetic resin layers are used as a single layer of each resin or as a laminate of two or more types. These synthetic resin layers preferably have good transparency (light transmittance).

It is also possible to provide a light-shielding layer (light-shielding layer) such as a metal foil such as an aluminum foil, an aluminum vapor-deposited film, a laminated film of a metal foil and a synthetic resin film, and a synthetic resin film into which a pigment is kneaded. it can. Among these light-shielding layers, aluminum foil and aluminum-deposited film have not only light-shielding properties but also moisture-proof, oil-resistant, non-water-absorbing properties, etc. It is preferable in giving properties such as long-term storage stability of the product.

(Multilayer Container) The multilayer container of the present invention comprises at least two or more layers having different wall surfaces,
At least one of the layers is made of a thermoplastic saturated norbornene-based polymer. If two or more layers of different materials are included, two or more layers of the same type of material may be included. The thermoplastic saturated norbornene-based polymer layer may be any of the innermost layer, the intermediate layer, and the outermost layer of the multilayer container. Further, two or more layers such as an innermost layer and an intermediate layer, an intermediate layer and an outermost layer, or an innermost layer and an outermost layer may be included. Medical test tubes, medical cells,
For medical containers such as blood bags, infusion bags, drug bottles, test cells, etc., or food packaging containers in areas where elution of trace impurities or deterioration in quality due to moisture is a problem, the innermost layer is made of thermoplastic saturated norbornene. It is preferred to arrange a polymer layer.

The multilayer structure is not particularly limited as long as it includes a thermoplastic saturated norbornene-based polymer layer and a layer made of another material. Specific examples include the following structures. However, the thermoplastic saturated norbornene-based polymer is an NB layer, the gas barrier resin layer is a barrier layer,
Other resin layers are abbreviated as synthetic resin layers. (1) NB layer / barrier layer (2) NB layer / synthetic resin layer (3) NB layer / barrier layer / synthetic resin layer (4) NB layer / synthetic resin layer / barrier layer (5) NB layer / synthetic resin layer / Barrier layer / synthetic resin layer (6) synthetic resin layer / NB layer / barrier layer (7) synthetic resin layer / NB layer / barrier layer / synthetic resin layer (8) synthetic resin layer / barrier layer / NB layer / barrier layer / Synthetic resin layer (9) synthetic resin layer / barrier layer / synthetic resin layer / NB layer / synthetic resin layer / barrier layer / synthetic resin layer (10) barrier layer / NB layer / barrier layer (11) synthetic resin layer / NB layer / plastic layer (1 2) NB layer / synthetic resin layer / light-shielding layer (1 3) NB layer / barrier layer / light-shielding layer (1 4) NB layer / synthetic resin layer / light-shielding layer / plastic layer (1 5 ) NB layer / barrier layer / light shielding layer / synthetic resin layer ( 16 ) NB Layer / light-shielding layer / barrier layer A desired multilayer structure such as a multilayer structure including these multilayers can be adopted depending on the purpose of use. Also,
The barrier layer and the synthetic resin layer themselves may be a laminate of two or more layers. Further
In addition, as described later, an adhesive layer may be provided between the respective layers as necessary.
Can be arranged.

The multilayer container of the present invention is as follows when a specific example of the layer structure according to the application is shown. An infusion bag contains an aqueous solution of sugar or an aqueous solution of vitamins, amino acids, fats, etc., and can be infused. An NB layer is used as the innermost layer, and a barrier polyester, PVDC, EVOH, etc. A structure in which layers are stacked (NB layer / barrier layer) is preferable. The barrier layer may be the outermost layer, or another transparent synthetic resin layer may be laminated as the outermost layer (NB layer / barrier layer / synthetic resin layer).

By making the NB layer the innermost layer, there is no elution of trace impurities and no deterioration in quality due to moisture even when a chemical solution is stored. And by the said multilayer structure, it can be set as the multilayer container excellent in the water vapor permeation resistance and the gas barrier property, and compared with the conventional infusion bag made from PVC or PE,
It is possible to suppress or prevent a change in the composition such as the water content of the chemical solution and the deterioration of the chemical solution. Further, the multilayer structure is also suitable for a chemical bottle. As a blood bag such as a blood transfusion bag, for example, a multilayer structure (NB layer / PC) in which an NB layer is the innermost layer and a transparent synthetic resin layer such as polycarbonate is laminated.
Layer, etc.), a transparent bag having flexibility is obtained. Then, optical analysis of the contents can be performed from outside the bag. As a medical analysis cell, a multilayer structure (NB) in which at least the innermost layer is an NB layer and a synthetic resin layer having excellent optical characteristics such as PMMA having excellent transparency is laminated.
Layer / PMMA layer). In addition, as a container for detecting and analyzing the contents by an optical method,
The NB layer may be the innermost layer and a transparent synthetic resin layer may be laminated, or a transparent barrier layer may be laminated instead of the transparent resin layer.

In a medical container using a medical agent, deterioration can be prevented by disposing a light-shielding layer. In this case, if a part or all of the light-shielding layer can be peeled off, it is convenient as a container that also serves as a packaging, dissolving, and administration of a medical drug. For example, a multilayer structure of NB layer / light-shielding layer / barrier layer is adopted, and the NB layer and the light-shielding layer are thermally fused to be peeled off (peel-off) to prevent deterioration of the contained medicine due to light. In use, when the drug is dissolved in water and administered to a patient, if the light-shielding layer is peeled off, external observation is easy. In a food packaging container, for example, when a thermoplastic saturated norbornene-based polymer layer is disposed in a multilayer intermediate layer made of a synthetic resin, the water vapor permeability is improved, and the taste of foods such as miso, soy sauce, and mayonnaise is improved. Can be prevented from decreasing or changing.

The multilayer film or sheet of the present invention can be obtained by dry lamination, extrusion coating, coextrusion lamination (T-die method, inflation method), heat lamination, or the like, or a lamination method combining these methods. (Films and foils). In addition, a thermoplastic saturated norbornene-based polymer may be converted into a good solvent such as an alicyclic hydrocarbon-based solvent (eg, cyclopentane, cyclohexane, methylcyclohexanedecalin), an aromatic hydrocarbon-based solvent (eg, toluene, xylene, ethylbenzene), and chlorine. It is also possible to use a method of applying and drying as a solution dissolved in a chlorinated hydrocarbon solvent (chloroform, chlorobenzene, etc.) or a mixed solvent thereof, or a mixed solvent with another solvent.

In some cases, the lamination is not necessary depending on the structure or shape, but in many cases, an interlayer adhesive is required. Thermoplastic saturated norbornene-based polymer is a material that is difficult to bond, but is used for hard-to-adhesive films such as polyethylene, polypropylene, and polyethylene terephthalate, and is used for interlayer bonding with other materials. Many adhesives such as a solution type of rubber (chloroprene, SBR, butyl rubber, etc.) and a solution type of polyolefin modified with chlorinated or maleic anhydride can be used. Specific examples of such adhesives include, for example, “Metal Foil × Polyethylene” in “All Adhesives Application-Specific Data and Use Manual” (published by Overseas Technical Data Institute, published on July 31, 1976). "Adhesive", "Metal foil x polypropylene adhesive", "Metal foil x polyester adhesive", "Normal cellophane x Polyethylene adhesive", "Normal cellophane x Polypropylene adhesive"
It can be selected from those introduced as "normal cellophane x adhesive for polyester" and "adhesive for polyethylene / polypropylene" in consideration of transparency, adhesive strength, and method of use.

As a method for producing a multilayer container, a sheet forming method (thermoforming method) such as vacuum forming or pressure forming, a blow forming method such as multilayer co-extrusion blow molding, or a method of cutting multilayer films cut into a predetermined shape. Various methods such as a method of forming a bag or the like by heat-sealing or bonding the peripheral portion with an adhesive can be adopted. In the case of heat fusion, the innermost layer is N
It is preferable to use a B layer or a synthetic resin layer having heat sealing properties, such as PP, PE, or an ionomer resin. The shape of the multilayer container includes, for example, a bottle, a tube, a bag, and a cell, and is not limited. Further, in an infusion bag or the like, an outlet such as an infusion outlet may be provided. Further, a printed synthetic resin layer may be provided. Thermoplastic saturated norbornene-based polymer layer (NB
The thickness of the layer can be appropriately determined according to the purpose of use, but is usually 3 μm to 5 mm, preferably 5 μm to 2 m.
m, and 3 to 15 in the case of an infusion bag or the like.
It is desirable that the film has a thickness of 0 μm, preferably 5 to 100 μm, and more preferably 10 to 50 μm. N
If the thickness of the layer B is too small, the water vapor transmission resistance is not improved.

[0029]

EXAMPLES The present invention will be described more specifically with reference to examples, reference examples and comparative examples, but the present invention is not limited to the examples. [Example 1] 6-ethyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-Octahydronaphthalene (hereinafter abbreviated as "ETD") hydrogenated product of a ring-opened polymer [ number
Having an average molecular weight of 50,000, a degree of hydrogenation of almost 100%, and a glass transition temperature of 145 ° C.]
m; NB layer), polyvinylidene chloride film (thickness 2)
0 μm; Kurehalon (trade name, manufactured by Kureha Chemical Co., Ltd.) was laminated via an adhesive (trade name: Asahi Hot Melt CL, manufactured by Asahi Chemical Co., Ltd.) to form a multilayer film. This multilayer film is cut into a length of 17 cm and a width of 28 cm, and then the two cut multilayer films are cut so that the NB layer becomes an inner layer.
The peripheral portion was heat-sealed to prepare a 1-liter infusion bag. The light transmissivity of this infusion bag at a wavelength of 400 nm was 81%, indicating good transparency. When this infusion bag was subjected to steam sterilization at 121 ° C. for 30 minutes, no cloudiness due to water absorption whitening was observed.

Example 2 A film made of the same hydrogenated product of the ring-opening polymer of ETD as in Example 1 and a film of polycarbonate (PC; trade name: Lexan 131-111 manufactured by GE) were added to an adhesive (Sunstar). Through the chemical company penguin cement 80D)
Lamination was performed to prepare a multilayer film having a hydrogenated product layer (NB layer) of 100 μm and a PC layer of 50 μm. This film is N
The peripheral portion was heat-sealed so that the layer B became the inner layer, thereby producing a 1-liter capacity blood bag. The light transmittance at a wavelength of 400 nm of this multilayer film is 80%,
It had sufficient transparency to perform optical analysis of the contents. Further, even when steam sterilization was performed, the NB layer did not whiten by water absorption.

Example 3 The same hydrogenated hydrogenated ring-opening polymer of ETD as in Example 1, polycarbonate (PC; trade name: Lexan 131-111, manufactured by GE), and ethylene-vinyl acetate copolymer (EVA; Sumitomo Chemical's product name Evatate)
Are blow molded, and the NB layer (about 200 μm) / EVA
Layer (approximately 100 μm) / PC layer (approximately 1 mm), and the NB layer is the innermost chemical bottle (internal volume 2
00 ml). This medicine bottle contains 80 g of nutrient powder ENM, sealed, and sealed at 40 ° C and 90% humidity.
For 100 days. Thereafter, the mixture was cooled, and the nutritional powder ENM was taken out and weighed. As a result, there was no change in weight and no change in water content was observed.

Example 4 The same hydrogenated product of the ring-opening polymer of ETD as in Example 1 and polymethyl methacrylate (PMMA; Acrypet manufactured by Mitsubishi Rayon Co., Ltd.) were coextruded to form an NB layer (200 μm).
A laminated film of / PMMA (200 μm) was prepared.
Next, this laminated film was vacuum-formed to prepare an analytical cell (test tube) having an inner volume of 2 ml and having an NB layer as an inner layer. The light transmittance at a wavelength of 400 nm of the wall surface of the cell for analysis was 80%, indicating excellent transparency.

Example 5 A film (thickness: 60 μm; NB layer) of a hydrogenated ring-opening polymer having the same ETD as in Example 1 was used as a light-shielding layer to a thickness of 10%.
A laminate film was prepared by laminating a laminate film of a polyester film having a thickness of 10 μm and an aluminum foil having a thickness of 10 μm, and a polyethylene film having a thickness of 60 μm. In addition, the polyester film and the polyethylene film of the light-shielding layer are adhered and integrated with each other,
The aluminum foil of the light-shielding layer and the NB layer are adhered so as to be peelable by heat fusion. Using this laminated film, a 1-liter infusion bag was prepared in the same manner as in Example 1. Since the innermost layer of this infusion bag is an NB layer and further has a light-shielding layer, there is no change in the quality of drugs such as nutrients and infusions. Furthermore, when dissolution or infusion of the drug, integral with the light-shielding layer and the polyethylene film layer N
By peeling off the layer B , the internal state can be observed.

Example 6 The same hydrogenated film of the ring-opening polymer of ETD as in Example 1 (thickness: 10 μm; NB layer), polyethylene film (thickness: 200 μm; PE layer), EV
A layer (20 μm thick; EVA layer), PE layer / NB layer / EVA layer / PE
A multilayer film consisting of layers was prepared and then vacuum-formed to prepare a 100 ml capacity mayonnaise container. This multilayer container was excellent in water impermeability and gas barrier properties, and did not change the content, decrease the taste, or change the water content even after long-term storage.

[0035]

According to the present invention, there is provided a medical or food packaging container having excellent resistance to water vapor transmission and having no change in composition such as the water content of the contents. Further, according to the present invention, a container having water vapor permeability and gas impermeability,
Alternatively, there is provided a container which is excellent in water vapor transmission resistance, has good transparency, does not have white turbidity due to water absorption whitening, and can detect components, composition, color, etc. of contents by an optical method.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B65D 81/24 A61J 1/00 331C 85/50 B65D 1 / 00B (56) References JP-A-51-115583 (JP, A JP-A-1-168724 (JP, A) JP-A-3-12835 (JP, A) JP-A-52-53983 (JP, A) JP-A-2-196832 (JP, A) 726 (JP, A) JP-A-57-68338 (JP, A) JP-B-60-34461 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61J 1/10 A23L 1 / 00 B32B 1/02 B32B 27/00 B65D 1/09 B65D 81/24 B65D 85/50

Claims (35)

(57) [Claims] 1. A container comprising a multilayer having at least two layers having different wall surfaces, wherein at least one of the multilayers is provided.
Layers Ri thermoplastic saturated norbornene-based polymer layer der, or
The thermoplastic saturated norbornene-based polymer is
Norbornene having a mer content of 30 mol% or less
Hydrogenated product of a ring-opening polymer of a monomer, the norbornene-based
Copolymer of monomer and ethylene, and water of the copolymer
Medical or food packaging containers, characterized in saturated polymer der Rukoto selected from hydrogen additive. 2. A hydrogenated product container of claim 1 wherein the saturated polymer a hydrogenation ratio of 90% or more. Is 3. A glass transition temperature of the thermoplastic saturated norbornene-based polymer is 100 ° C. or higher according to claim 1 or 2
The container as described. 4. to the number-average molecular weight of the thermoplastic saturated norbornene polymer claims 1 to 100,000 from 10,003
The container according to any one of claims 1 to 4. 5. A container according to to moisture absorption of the thermoplastic saturated norbornene polymer claims 1 0.01% or less any one of four. 6. A layer having a material different from that of the thermoplastic saturated norbornene-based polymer layer, wherein at least one layer has an oxygen transmission rate at 20 ° C. of 0.5 cc / m ² · 24 hr · at.
The container according to any one of claims 1 to 5 , comprising a multilayer including a gas barrier resin layer having a thickness of not more than m. As 7. thermoplastic saturated norbornene-based polymer layer and the different layers of material, a synthetic resin layer at least one layer (except for the gas barrier resin layer) any one of claims 1 made of a multilayer containing 6 The container according to claim 1. 8. A container according to any one of claims 1 to 7 light transmittance of 70% or more in the multi wavelength 400 nm. 9. As the different layers of a thermoplastic saturated norbornene polymer layer material container according to any one of claims 1 made of a multilayer 7 including the light-shielding layer of at least one layer. 10. The container according to claim 9, wherein the multilayer has a light transmittance at 400 nm of less than 10%. 11. at least a portion container according to claim 9 or 10, wherein is releasably laminated light-shielding layer. 12. shielding layer is a metal foil, aluminum deposition film, according to any one of the laminate film according to claim 9 to 11 or a synthetic resin film kneaded with a pigment, a metallic foil and a synthetic resin film Container. 13. A container according to any one of claims 1 to 12 the innermost layer of the container wall is a thermoplastic norbornene-based polymer layer. 14. The container according to any one of claims 1 to 13 are arranged the adhesive layer as needed between the layers. 15. The sheet molding, blow molding, thermal fusion bonding method or container according to any one of claims 1 and is formed by a bonding method 14 with an adhesive. 16. A medical test tube, a medical cell,
The container according to any one of claims 1 to 15 , which is a blood bag, an infusion bag, a medicine bottle, or a test cell. 17. A multilayer film or sheet comprising a that at least two layers of different materials, Ri least one layer thermoplastic saturated norbornene-based polymer layer der of them,
In addition, the thermoplastic saturated norbornene-based polymer
Norbornene having a nomer content ratio of 30 mol% or less
Hydrogenated product of a ring-opening polymer of a series monomer,
Copolymer of ethylene-based monomer and ethylene, and the copolymer
Ru saturated polymer der selected from a hydrogenated product multilayer film or sheet. 18. The multilayer film or sheet according to claim 17 , wherein the hydrogenated product is a saturated polymer having a hydrogenation ratio of 90% or more. 19. The thermoplastic claim a glass transition temperature of 100 ° C. or more saturated norbornene-based polymer 17 also
19. The multilayer film or sheet according to item 18 . 20. A multilayer film or sheet according to any one of claims 17 <br/> to 19 number average molecular weight of the thermoplastic saturated norbornene polymer is 100,000 from 10,000. 21. to moisture absorption of the thermoplastic saturated norbornene polymer claims 17 or less 0.01% 20
The multilayer film or sheet according to any one of the above. 22. A layer made of a material different from that of the thermoplastic saturated norbornene-based polymer layer, wherein at least one layer has an oxygen transmission rate at 20 ° C. of 0.5 cc / m ² · 24 hr · a.
claim containing gas barrier resin layer is tm or less 17
22. The multilayer film or sheet according to any one of claims 21 to 21 . As different layers 23. Thermoplastic saturated norbornene polymer layer and the material, synthetic resin layer at least one layer (except for the gas barrier resin layer) in any one of claims 17 contains 22 A multilayer film or sheet as described. 24. The multilayer film or sheet according to claim 23 , comprising a layer structure of a thermoplastic saturated norbornene-based polymer layer / synthetic resin layer. 25. Synthetic resin layer / heat claim 23 comprising a layer structure of the thermoplastic saturated norbornene polymer layer / plastic layer
A multilayer film or sheet as described. 26. The thermoplastic saturated norbornene polymer layer and the different layers of materials, multi-layer film or sheet according to any one of claims 17 to 25 including the light-shielding layer of at least one layer. 27. The multilayer film or sheet according to claim 26 , wherein the light-shielding layer is a metal foil, an aluminum vapor-deposited film, a laminated film of a metal foil and a synthetic resin film, or a synthetic resin film into which a pigment is kneaded. 28. The multilayer film or sheet according to claim 27 , wherein the metal foil is an aluminum foil. 29. A thermoplastic norbornene-based polymer layer /
Claim 27 or 2 comprising a layer structure of the light-shielding layer / plastic layer
9. The multilayer film or sheet according to 8 . 30. A multilayer film or sheet according to any one of claims 17 to 29, the adhesive layer as needed between the layers are arranged. 31. The multilayer film or sheet according to claim 30, which has a layer structure of a thermoplastic saturated norbornene-based polymer layer / adhesive layer / gas barrier resin layer. 32. The multilayer film or sheet according to claim 30, which has a layer structure of a thermoplastic saturated norbornene-based polymer layer / adhesive layer / synthetic resin layer. 33. The multilayer film or sheet according to claim 30, which has a layer structure of a synthetic resin layer / adhesive layer / thermoplastic saturated norbornene-based polymer layer / adhesive layer / synthetic resin layer. 34. The multilayer film or sheet according to claim 30, which has a layer structure of a thermoplastic saturated norbornene-based polymer layer / adhesive layer / light-shielding layer. 35. It does not claim 17, which is a multilayer container 3
5. The multilayer film or sheet according to any one of the above items 4 .