JPH06171040A - Polyolefin-based base material for medical container - Google Patents

Abstract

PURPOSE:To provide polyolefin-based base material for medical container, which is equipped with enough heat resistance withstanding medical high pressure steam sterilization and excellent in flexibility, transparency and the like. CONSTITUTION:Polyolefin-based base material for medical container concerned is multi-layered body consisting of crystalline copolymer layer made of or mainly made of crystalline polypropylene and/or crystalline polybutene-1 and polypropylene-based amorphous polymer-containing layer. The layer made of crystalline copolymer made of or mainly made of crystalline polypropylene and/or crystalline polybutene-1 is employed as the innermost and outermost layers of the polyolefin-based base material for medical container concerned.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin-based medical container base material suitable for containers for storing liquids such as blood and liquid medicines used in the medical field, and for carrying tubes (connection pipes) and the like.

2. Description of the Related Art Materials for containers and tubes used in medical treatment such as blood collection, blood transfusion, and liquid transfusion are required to have various performances in addition to safety and hygiene. Among them, flexibility, transparency, heat resistance and The balance of is an important item. Conventionally, as the polymer material for the above-mentioned applications, soft polyvinyl chloride, and ethylene-vinyl acetate copolymer, and polyethylene-based polymers such as low-density polyethylene are typical examples. Etc. may cause problems. In the case of polyethylene type, the balance between flexibility / transparency and heat resistance is lacking, and low density products have relatively good flexibility / transparency, but the melting point inevitably becomes low, so the heat resistance decreases, usually 100- Thirteen
It cannot withstand high-pressure steam sterilization performed at 0 ° C, and is likely to cause blocking, devitrification (whitening), avatar-like unevenness, deformation, and the like. Chemical cross-linking, radiation cross-linking and the like are available as methods for increasing heat resistance, but the production process is inevitably complicated. Polypropylene is also a polymer widely used in medical containers, and its good heat resistance is far more advantageous than polyethylene. However, polypropylene is also a polymer in which it is difficult to obtain a transparent molded product and has high rigidity (poor flexibility), which limits its use. Other than the above, polybutene-1 is also a polyolefin that is relatively flexible, and is noted, but it has a defect that transparency is not sufficient.

SUMMARY OF THE INVENTION The present invention has been made to provide a substrate for a medical container in which the above-mentioned problems of the prior art have been solved.

As a result of various investigations, the present inventors have found that the specific use of amorphous polypropylene is suitable for the purpose, and crystalline polypropylene and / or crystalline polybutene-1 or a main component thereof is used. And a layer containing a crystalline copolymer (A) and a layer containing a polypropylene-based amorphous polymer (B), wherein (A) forms an innermost layer and an outermost layer. The present invention has been made, in which the main component is a polyolefin-based medical container substrate. Of (A) in the present invention, crystalline polypropylene or a crystalline copolymer containing the crystalline polypropylene as a main component (hereinafter referred to as polypropylene-based crystalline polymer)
Is a polymer containing isotactic or syndiotactic type polypropylene as a main component, which is usually obtained by using a stereoregular polymerization catalyst. These are appropriately selected, but a copolymer, particularly a copolymer rich in randomness, is advantageous in order to meet the purpose of improving the transparency of the present invention and to meet the demand for softening medical containers. As the comonomer, α-olefins having 2 to 12 carbon atoms such as ethylene, butene-1, pentene-1, hexene-1, octene-1, decene-1, dodecene-1,4-methylpentene-1 are preferable, and the comonomer is a comonomer. The amount is about 3 to 40 mol%, more preferably about 5 to 30 mol%. A particularly preferred polypropylene-based crystalline polymer has a flexural modulus (J
ISK7203) has a Vicat softening point (JISK7206) of 100 ° C or higher and a Vicat softening point (JISK7206) of 6000 kg / cm ² or less, which is preferable in terms of the balance of flexibility, transparency, and heat resistance. The polypropylene-based crystalline polymer has a MFR (melt flow rate) of 0.3 to 40, more preferably 0.5 to 30 at a temperature of 230 ° C. and a load of 2,160 kg in view of moldability and mechanical properties of the molded product. Good to have. In (A), crystalline polybutene-1 or a crystalline copolymer having the same as the main component (hereinafter referred to as polybutene-1 type crystalline polymer) is so-called isotactic polybutene-1 or a copolymer having the same as the main component. And is usually produced by a known method. In the case of copolymers, the comonomers used are ethylene, propylene, pentene-1, hexene-1, octene-1,4-.
Α-Olefins such as methylpentene-1 are preferred. These are introduced in order to improve the flexibility and transparency of polybutene-1, but if the melting point (the melting point of homopolybutene-1 is 125 to 130 ° C.) is too low, the heat resistance will be poor, so that The amount introduced is about 10 mol% or less,
More preferably, it should be suppressed to 5 mol% or less. And considering the moldability and mechanical properties of the product, polybutene-1
The crystalline polymer has a MFR at a temperature of 190 ° C. and a load of 2,160 g of 0.2 to 30, and more preferably 0.5 to 2.
5 is good. The polypropylene-based crystalline polymer and the polybutene-1-based crystalline polymer are excellent in compatibility and miscibility at arbitrary ratios, and therefore (A) may be composed of both components. Next, the polypropylene-based amorphous polymer (B) in the present invention
Is an amorphous atactic polypropylene or a copolymer containing it as a main component, which is produced as a by-product in the production process of the polypropylene-based crystalline polymer described in (A), and can be produced by radical polymerization or the like. In the case of copolymer (A)
A comonomer similar to that in is used. The polypropylene-based amorphous polymer used in the present invention has a melt viscosity at 190 ° C. of 300 to 1
0,000 cps, more preferably 500-80,000
0 cps, softening point measured by ring and ball method of 100-160
C., and more preferably 110 to 150.degree. As described at the beginning, the present invention is a multilayer body including a layer composed of (A) and a layer containing (B). Here, the "layer containing (B)" means that the layer is This means that it may be composed of (B) alone or may be composed of a polymer composition containing (B) as one component. The polymer composition as used in controlling the mechanical properties (flexibility, strength, etc.), gas (water vapor, oxygen, etc.) permeability, moldability, etc. of the multilayer body is used. From the viewpoint of miscibility and compatibility, the polymer composition of (A) and (B) is recommended as the composition of this polymer composition, and the weight ratio of (A) and (B) is 30: 7.
0 to 90:10, more preferably 40:60 to 80: 2
0 is preferable ((A) and (B) are compatible at any ratio). Further, the “innermost layer” and the “outermost layer” referred to in the present invention are “a layer forming an inner wall surface of a container or a tube” and “a layer forming an outer wall surface of a container or a tube”, respectively. Needless to say, (A) may form part of the intermediate layer. The reason that the medical container substrate of the present invention has the layer (B) as the intermediate layer and the layer (A) constitutes the innermost layer and the outermost layer is because the amorphous polypropylene-based polymer in the layer (B) is highly adhesive. If the (B) layer exists in the innermost layer or the outermost layer, the sheet (container) or the tube may cause blocking. The present inventors have proposed “Japanese Patent Application No. 4-74342” for “a medical container base material comprising a polymer composition of (A) and (B)”. By doing so, it becomes a more versatile substrate for medical containers. The most common and simple structure is a type (three-layer structure type) in which the innermost layer and the outermost layer are (A) layers, and one layer sandwiched between these layers is a (B) layer, but more than that The multi-layer structure type, for example, a 5-layer type or a 7-layer type may be used. In addition, the properties required for applications of medical container base materials are:
Generally, the base material has a total thickness of 50 to 1,000 μm, more preferably 80 to 800 μm, although it depends on the properties of (A) and (B) and the like.
Each layer is 5 to 100 μm, more preferably 10 to 8
It is preferably 0 μm. Next, in the present invention, a medical container means a container (including a bag) or a tube for storing or transporting a liquid to be treated in medicine such as blood and medical liquid, and such a product can be obtained by a generally known method. In the case of a container, (A) and (B) are heated to a temperature above the flow initiation temperature, preferably 170 to 260 ° C, more preferably 17
Extrusion at 5 to 255 ° C. through a T-die for multilayer extrusion or a tubular die for multilayer extrusion (it is desirable to cool the casting roller or sheet with water to suppress crystallization),
The obtained flat sheet, tubular sheet, parison or the like may be processed into a predetermined thickness or shape by appropriately utilizing techniques such as thermoforming, blowing, stretching, cutting, and heat sealing. Further, it may be in a non-stretched state or a stretched state. In the case of tubes, the extrusion method is the most suitable. Roughening (embossing) of the inner surface or outer surface of the container or tube for the purpose of improving the blocking resistance, addition of a slip agent, an anti-blocking agent, etc. may be performed without departing from the scope of the present invention. The polymer, the plasticizer, the inorganic filler, the stabilizer and the like may be added, and (B) may be processed into (A) of the innermost layer or the outermost layer as long as the blocking phenomenon does not occur.
Here, as the "other polymer", a thermoplastic elastomer such as SEPS (block copolymer of polystyrene and ethylene propylene copolymer), SEBS (block copolymer of polystyrene and ethylene butylene copolymer) or C9 is used in the portion (A) or (B). The addition of hydrogenated synthetic petroleum resin is effective because the transparency and flexibility are further improved. If necessary, for example, polyethylene, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinylidene chloride, nylon 6, nylon 12, polyethylene terephthalate, polybutylene terephthalate, for improving gas barrier properties, heat sealing properties and mechanical properties. It is also possible to further laminate polyurethane or the like on the multilayer body of the present invention. The base material of the present invention is useful as a blood component storage container and also as a container for physiological saline, electrolyte solution, dextran preparation, mannitol preparation, saccharide preparation, amino acid preparation and the like.

The present invention will be described in more detail with reference to the following examples. The sheets (films) used here are all unstretched products. (1) Experimental method Polymers used: The copolymers (or polymer compositions) shown in Table 1 were used in combination. Preparation of sheet: The pellets were melted separately in an extruder and supplied to a two-kind three-layer T-die (lip length 400 mm, lip width 0.8 mm), and a sheet having (B) as an intermediate layer was 180 to 220 ° C. After cooling with a casting roller kept at 15 ° C., trimming was performed and a sheet having a thickness of about 320 μm and a width of 300 mm was wound at a speed of 6 m / min. Measurement of Transparency of Sheet: The water transmittance of the sheet obtained in 4. at a wavelength of 450 nm was measured with a Shimadzu double beam type self-recording spectrophotometer UV-300.
Measurement of flexibility of sheet: The sheet obtained in the above was cut into a dumbbell shape and the tensile elastic modulus was measured according to JIS K7113, and used as a measure of flexibility. High-pressure steam sterilization test: 150 sheets obtained in
It was cut into a size of mm × 250 mm, and two sheets of this were stacked and heat-sealed to form a bag, and 800 ml of physiological saline was put therein and sealed. This container containing the chemical solution was placed in a retort type high-pressure steam sterilizer, and the temperature was 115 ° C and the gauge pressure was 1.8 kg /
It was processed under the conditions of cm ² and time of 25 minutes. After cooling to room temperature and leaving for 48 hours, the bag was inspected for appearance such as transparency and shape. Heavy metal and eluate test: The sheet obtained in accordance with the Japanese Pharmacopoeia general test method “Plastic container test method for infusion” was tested.

[Table 1]

[Table 2] (2) Experimental results (see Table 2) Extrusion molding of the sheet was successful, and foreign matter, foaming, blocking, etc. were not observed in any of the compositions, and a highly uniform sheet was obtained. It was confirmed that the heavy metals and eluates were compatible with the Japanese Pharmacopoeia in any composition. The appearance of the container after the high-pressure steam sterilization treatment was almost the same as that before the sterilization treatment in any composition. As shown in Table 2 for the relationship between the composition, the light transmittance of the sheet, and the tensile modulus, (A) is the innermost layer and the outermost layer,
It can be seen that the sheet having (B) as the intermediate layer has good transparency and flexibility.

As described above, in the medical container base material of the present invention, the problem of the layer containing the polypropylene-based amorphous polymer is that crystalline polypropylene and / or crystalline polybutene-1 or these are the main components. It is one that skillfully utilizes the effect solved by coating with a layer composed of the crystalline copolymer, and is useful as a base material for containers for blood, pharmaceutical liquids and the like. Further, since it has good moldability, it has a high industrial value.

[Procedure amendment]

[Submission date] December 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title of the invention: Base material for polyolefin medical container

[Claims]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin-based medical container base material suitable for containers for storing liquids such as blood and liquid medicines used in the medical field, and for carrying tubes (connection pipes) and the like.

[0002]

2. Description of the Related Art Materials for containers and tubes used in medical treatment such as blood collection, blood transfusion, and liquid transfusion are required to have various performances in addition to safety and hygiene. Among them, flexibility, transparency, heat resistance and The balance of is an important item. Conventionally, as the polymer material for the above-mentioned applications, soft polyvinyl chloride, and ethylene-vinyl acetate copolymer, and polyethylene-based polymers such as low-density polyethylene are typical examples. Etc. may cause problems. In the case of polyethylene type, the balance between flexibility / transparency and heat resistance is lacking, and low density products have relatively good flexibility / transparency, but the melting point inevitably becomes low, so the heat resistance decreases, usually 100- Thirteen
It cannot withstand high-pressure steam sterilization performed at 0 ° C, and is likely to cause blocking, devitrification (whitening), avatar-like unevenness, deformation, and the like. Chemical cross-linking, radiation cross-linking and the like are available as methods for increasing heat resistance, but the production process is inevitably complicated. Polypropylene is also a polymer widely used in medical containers, and its good heat resistance is far more advantageous than polyethylene. However, polypropylene is also a polymer in which it is difficult to obtain a transparent molded product and has high rigidity (poor flexibility), which limits its use.

Other than the above, polybutene-1 is also a polyolefin which is relatively flexible, and is noted, but it has a defect that transparency is not sufficient.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to provide a substrate for a medical container in which the above-mentioned problems of the prior art have been solved.

[0005]

As a result of various investigations, the present inventors have found that the specific use of amorphous polypropylene is suitable for the purpose, and crystalline polypropylene and / or crystalline polybutene-1 or a main component thereof is used. And a layer containing a crystalline copolymer (A) and a layer containing a polypropylene-based amorphous polymer (B), wherein (A) forms an innermost layer and an outermost layer. The present invention has been made, in which the main component is a polyolefin-based medical container substrate.

Among (A) in the present invention, crystalline polypropylene or a crystalline copolymer containing the crystalline polypropylene as a main component (hereinafter referred to as polypropylene-based crystalline polymer) is an isotactic compound usually obtained by using a stereoregular polymerization catalyst. Alternatively, it is a polymer whose main component is syndiotactic polypropylene. These are appropriately selected, but a copolymer, particularly a copolymer rich in randomness, is advantageous in order to meet the purpose of improving the transparency of the present invention and to meet the demand for softening medical containers.

The comonomers include ethylene and butene.
Α-olefins having 2 to 12 carbon atoms such as 1, pentene-1, hexene-1, octene-1, decene-1, dodecene-1, 4-methylpentene-1 are preferable, and the comonomer amount is 3 to 40 mol%. Degree, more preferably 5 to 30
About mol% is suitable.

A particularly preferred polypropylene-based crystalline polymer has a flexural modulus (JISK7203) of 6,000.
kg / cm ² or less in Vicat softening point (JISK720
6) is 100 ° C. or higher, which is preferable in terms of the balance of flexibility, transparency, and heat resistance. The polypropylene-based crystalline polymer has a MFR (melt flow rate) of 0.3 to 40, more preferably 0.5 to 30 at a temperature of 230 ° C. and a load of 2,160 kg in view of moldability and mechanical properties of the molded product. Good to have.

Further, among (A), crystalline polybutene-1
Alternatively, a crystalline copolymer containing the same as the main component (hereinafter referred to as polybutene-1 type crystalline polymer) means so-called isotactic polybutene-1 or a copolymer containing the same as the main component, and is usually produced by a known method. There is. In the case of copolymers, the comonomers used are ethylene, propylene, pentene-1, hexene-1, octene-1, 4,
Α-Olefins such as -methylpentene-1 are preferred. These are introduced in order to improve the flexibility and transparency of polybutene-1, but if the melting point (the melting point of homopolybutene-1 is 125 to 130 ° C.) is too low, the heat resistance will be poor, so that The amount introduced is about 10 mol% or less,
More preferably, it should be suppressed to 5 mol% or less. And considering the moldability and mechanical properties of the product, polybutene-1
The crystalline polymer has a MFR at a temperature of 190 ° C. and a load of 2,160 g of 0.2 to 30, and more preferably 0.5 to 2.
5 is good.

Since the polypropylene-based crystalline polymer and the polybutene-1-based crystalline polymer are excellent in compatibility and miscibility at any ratio, (A) may be composed of both components.

Next, the polypropylene-based amorphous polymer (B) in the present invention is amorphous atactic polypropylene or a copolymer containing this as a main component,
In addition to the by-product in the process of producing the polypropylene-based crystalline polymer described in (A), it can be produced by radical polymerization or the like.
In the case of copolymers, the same comonomers as in (A) are used.

The polypropylene type amorphous polymer used in the present invention has a melt viscosity at 190 ° C. of 300 to 100,000 cps, more preferably 500 to 80,000 cps, and a softening point of 100 to 160 ° C. measured by a ring and ball method. , And more preferably 110 to 150
It may be in ° C.

As described at the beginning, the present invention is a multilayer body including a layer comprising (A) and a layer containing (B),
Here, the "layer containing (B)" means that the layer may be composed of (B) alone or may be composed of a polymer composition containing (B) as one component. The polymer composition as used in controlling the mechanical properties (flexibility, strength, etc.), gas (water vapor, oxygen, etc.) permeability, moldability, etc. of the multilayer body is used. From the viewpoint of miscibility and compatibility, the polymer composition of (A) and (B) is recommended for the constitution of this polymer composition, and the weight ratio of (A) and (B) is 3
0:70 to 90:10, more preferably 40:60 to 8
0:20 is preferable ((A) and (B) are compatible at any ratio).

The "innermost layer" and "outermost layer" referred to in the present invention are "layer forming the inner wall surface of a container or tube" and "layer forming the outer wall surface of a container or tube", respectively. Needless to say, (A) may form part of the intermediate layer.

The reason that the medical container substrate of the present invention uses the layer (B) as an intermediate layer and the layer (A) constitutes the innermost layer and the outermost layer is because the amorphous polypropylene-based polymer in the layer (B) is tacky. This is because if the (B) layer is present in the innermost layer or the outermost layer, the sheet (container) or the tube may cause blocking. The present inventors have stated that “(A)
A "base material for a medical container comprising a polymer composition of (1) and (B)" is proposed in Japanese Patent Application No. 4-74342, but a medical container having more general versatility by using the constitution of the present invention. It becomes the base material.

The most common and simple structure is a type (three-layer structure type) in which the innermost layer and the outermost layer are (A) layers, and one layer sandwiched between these layers is a (B) layer. ,
A multilayer structure type of more than that, for example, a 5-layer type or a 7-layer type, may be used. Further, the properties required for the use of the medical container base material vary depending on the properties (A) and (B), etc., but in general, the base material has an overall thickness of 50 to 1,
000 μm, more preferably 80 to 800 μm, the innermost layer and the outermost layer (A) are each 5 to 100 μm,
More preferably, it is 10 to 80 μm.

The term "medical container" as used in the present invention means a container (including a bag) or a tube for storing or transporting a liquid such as blood or a medical liquid to be used in medical treatment. Such a product is manufactured by a known method. can get. For containers,
(A) and (B) are extruded at a temperature equal to or higher than the flow initiation temperature, preferably 170 to 260 ° C., more preferably 175 to 255 ° C., through a T die for multilayer extrusion or a tubular die for multilayer extrusion (casting roller or It is desirable to cool the sheet with water to suppress crystallization), and appropriately apply techniques such as thermoforming, blowing, stretching, cutting, and heat sealing to the obtained flat sheet, tubular sheet, parison, etc. And processed into a predetermined thickness and shape. Further, it may be in a non-stretched state or a stretched state.
In the case of tubes, the extrusion method is the most suitable. Roughening (embossing) of the inner or outer surface of the container or tube for the purpose of improving the blocking resistance, addition of a slip agent, an anti-blocking agent, etc. may be performed without departing from the scope of the present invention. The polymer, the plasticizer, the inorganic filler, the stabilizer, etc. may be added, and (B) may be processed into (A) of the innermost layer or the outermost layer within the range where the blocking phenomenon does not occur.

Here, as the "other polymer", SEPS (block copolymer of polystyrene and ethylene propylene copolymer) or SEB is added to the portion (A) or (B).
Thermoplastic elastomer such as S (block copolymer of polystyrene and ethylene butylene copolymer) or C
It is effective to add a hydrogenated product of a 9-type synthetic petroleum resin, because transparency and flexibility are further improved.

If necessary, for example, gas barrier property,
In order to improve heat sealability and mechanical properties, polyethylene, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinylidene chloride, nylon 6, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polyurethane and the like are further added to the multilayer body of the present invention. It may be laminated.

The substrate of the present invention is useful as a container for storing blood components and as a container for physiological saline, electrolyte solution, dextran preparation, mannitol preparation, saccharide preparation, amino acid preparation and the like.

[0021]

The present invention will be described in more detail with reference to the following examples. The sheets (films) used here are all unstretched products.

(1) Experimental Method Polymers used: The copolymers (or polymer compositions) shown in Table 1 were used in combination.

Preparation of sheet: The pellets of (3) were separately melted by an extruder and melted in a two-kind three-layer type T-die (lip length 4
00 mm, lip width 0.8 mm) and extruding a sheet having (B) as an intermediate layer at 180 to 220 ° C. and 15 ° C.
After cooling with a casting roller kept at, trimmed and trimmed a sheet with a thickness of 320 μm and a width of 300 mm to 6 m.
It was wound up at a speed of / minute.

Measurement of Transparency of Sheet: With respect to the sheet obtained in the above, the transmittance in water at a wavelength of 450 nm was measured with a Shimadzu double beam type self-recording spectrophotometer UV-300. Measurement of flexibility of sheet: The sheet obtained in the above was cut into a dumbbell shape and the tensile elastic modulus was measured according to JIS K7113, and used as a measure of flexibility.

High pressure steam sterilization test: The sheets obtained in the high pressure steam sterilization test were cut into a size of 150 mm × 250 mm, two sheets were stacked and heat-sealed to prepare a bag, and 800 ml of physiological saline was put therein and sealed. The container containing the chemical solution was placed in a retort type high-pressure steam sterilizer and treated under the conditions of a temperature of 115 ° C., a gauge pressure of 1.8 kg / cm ² , and a time of 25 minutes. After cooling to room temperature and leaving for 48 hours, the bag was inspected for appearance such as transparency and shape.

Heavy metal and eluate test: The sheet obtained in accordance with the Japanese Pharmacopoeia general test method "Plastic container test method for infusion" was tested.

[0027]

[Table 1]

[0028]

[Table 2]

(2) Experimental Results (See Table 2) Extrusion molding of the sheet was successful, and no foreign matter, foaming, blocking, etc. were observed in any of the compositions, and a highly uniform sheet was obtained.

It was confirmed that the heavy metals and the eluates were compatible with the Japanese Pharmacopoeia in any composition.

The appearance of the container after the high-pressure steam sterilization treatment was almost the same as that before the sterilization treatment in any composition.

As shown in Table 2 for the relationship between the composition and the light transmittance and tensile modulus of the sheet, the sheet having (A) the innermost layer and the outermost layer and (B) the intermediate layer has good transparency. It turns out that it has flexibility.

[0033]

As described above, in the medical container base material of the present invention, the problem of the layer containing the polypropylene-based amorphous polymer is that crystalline polypropylene and / or crystalline polybutene-1 or these are the main components. It is one that skillfully utilizes the effect solved by coating with a layer composed of the crystalline copolymer, and is useful as a base material for containers for blood, pharmaceutical liquids and the like. Further, since it has good moldability, it has a high industrial value.

Claims (1)

[Claims] 1. A composite comprising a layer comprising crystalline polypropylene and / or crystalline polybutene-1, or a crystalline copolymer (A) containing these as the main components, and a layer comprising a polypropylene-based amorphous polymer (B). A layered body, wherein (A) forms an innermost layer and an outermost layer, a polyolefin-based substrate for a medical container.