JP6492498B2 - Medical packaging material, medical packaging container comprising the same, and manufacturing method thereof - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a medical packaging material, a medical packaging container comprising the same, and a method for producing the same, and more particularly, medical treatment that exhibits high interlayer adhesive strength and low elution and maintains this even after heat sterilization treatment. The present invention relates to a packaging material for medical use, a medical packaging container comprising the same, and a method for producing the same.

As a packaging material for filling and packaging pharmaceuticals, food / beverage products, cosmetics, chemical products and the like, a packaging material composed of a laminate in which a base material layer and a sealant layer are laminated via an adhesive layer is used. Here, in order to obtain a high interlayer adhesion strength, a method of laminating by a dry laminating method using a dry laminating adhesive such as a two-component curable urethane adhesive is generally known as an adhesive layer. (Patent Document 1).
However, the packaging material obtained by this method has a problem that, due to long-term storage, the components in the contents erode the adhesive layer through the sealant layer, and the bond of the adhesive is decomposed to lower the interlayer adhesive strength. It was. In addition, low molecular weight substances such as unreacted monomers and decomposition products are eluted from the eroded adhesive layer, and there is a problem that the content is contaminated although the amount is small. It is known that such erosion of the adhesive layer is more likely to proceed after the retort sterilization treatment performed under high temperature and pressure.
Therefore, the above-mentioned problem is a serious problem particularly in packaging materials such as pharmaceutical / medical packaging materials, which require reliable gas barrier properties and severe low elution over a long period of time and can be subjected to retort sterilization treatment. .

Japanese Patent Laid-Open No. 5-51574

  The present invention has been made to solve such a problem, and exhibits a high interlayer adhesive strength and a low elution property, and a medical packaging material that maintains this even after heat sterilization treatment, and a medical packaging container comprising the same, An object of the present invention is to provide a manufacturing method thereof.

  As a result of various studies, the inventor has at least a base material layer, an adhesive layer, and a heat-sealable resin layer in this order, and the adhesive layer is composed of alkene- (meth) acrylate ester-unsaturated carboxylic acid. It has been found that a medical packaging material comprising an adhesive resin composition containing an original copolymer achieves the above object.

The present invention is characterized by the following points.
(1) It has at least a base material layer, an adhesive layer, and a heat-sealable resin layer in this order, and the adhesive layer contains an alkene- (meth) acrylate-unsaturated carboxylic acid terpolymer. A medical packaging material comprising a functional resin composition.
(2) The medical packaging material according to (1) above, further comprising a barrier layer between the base material layer and the adhesive layer.
(3) The unsaturated carboxylic acid component amount in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass, as described in (1) or (2) above Medical packaging material.
(4) The medical packaging according to any one of (1) to (3) above, wherein the amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass. material. (5) The medical packaging material according to any one of (1) to (4), wherein the heat-sealable resin layer is a layer made of a polyolefin-based resin.
(6) The medical packaging material which overlaps the medical packaging material in any one of said (1)-(5) so that the heat-sealable resin layers may oppose, and heat-seals the edge part. container.
(7) The interlayer adhesion strength after heat sterilization treatment at 105 ° C. for 30 minutes is maintained at 60% or more, more preferably 70% or more with respect to the interlayer adhesion strength before the heat sterilization treatment, The medical packaging container according to (6) above.
(8) The interlayer adhesion strength after heat sterilization treatment at 121 ° C. for 25 minutes is maintained at 60% or more, more preferably 70% or more, with respect to the interlayer adhesion strength before the heat sterilization treatment. The medical packaging container according to the above (6) or (7).
(9) The medical packaging container according to any one of the above (6) to (8), which satisfies the elution test standard of the Japanese Pharmacopoeia plastic drug container test method.
(10) The method for producing a medical packaging material according to any one of (1) to (5) above, wherein the base material layer or the barrier layer and the heat-sealable resin layer are alkene- (meth) acrylic. The production method according to the above, wherein lamination is performed by a sandwich lamination method through a molten adhesive resin composition containing an acid ester-unsaturated carboxylic acid terpolymer.

  The medical packaging material of the present invention exhibits excellent low elution, that is, mixing of low molecular weight substances into the contents is suppressed, and extremely high interlayer adhesion strength can be achieved. Furthermore, the medical packaging material of the present invention can maintain high interlayer adhesion strength even after being subjected to heat sterilization treatment such as boil treatment or retort treatment. Therefore, the packaging material of the present invention can be suitably used as a medical packaging container or the like that requires high low elution properties and interlayer adhesion strength.

It is the schematic cross section which showed an example of the layer structure of the packaging material of this invention. It is the schematic cross section which showed the other example of the layer structure of the packaging material of this invention.

  The present invention will be described in more detail below. Hereinafter, the resin names used in the present invention are those commonly used in the industry.

<1> Layer structure of packaging material of the present invention The packaging material of the present invention will be described in detail with reference to the drawings.
1 and 2 are schematic cross-sectional views showing an example of the layer structure of the packaging material of the present invention.
As shown in FIG. 1, the packaging material of the present invention has a basic structure in which a base material layer 1 and a heat-sealable resin layer 3 are laminated via an adhesive layer 2. Here, the adhesive layer 2 is a layer made of an adhesive resin composition containing an alkene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer.

The packaging material of the present invention may have a barrier layer 4 between the base material layer 1 and the adhesive layer 2 as shown in FIG.
The packaging material of the present invention includes an adhesive resin composition containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer, a film constituting the base material layer 1 or the barrier layer 4, a heat It can laminate | stack by melt extrusion, ie, the sandwich lamination method, between the films which comprise a sealing resin layer.

Alternatively, an adhesive resin composition containing a molten alkene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer is melted on the film constituting the base layer 1 or the barrier layer 4. You may laminate | stack by coextrusion coating with sealing resin.
Since the penetration of the components in the contents stops at the barrier layer 4, the base material layer 1 and the barrier layer 4 can be laminated by any lamination method such as a dry lamination method, a sandwich lamination method, and an extrusion coating method.
If necessary, additional layers such as a printing layer, an intermediate layer, and a reinforcing layer can be provided at any position, for example, between the base material layer 1 and the adhesive layer 2 or outside the base material layer 1. .
Next, the material etc. which comprise the laminated body of this invention are demonstrated.

<2> Base material layer In this invention, the film which comprises a normal packaging material can be used suitably as a base material layer. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polyvinyl alcohol, polyacrylonitrile, polycarbonate, ethylene-vinyl acetate copolymer, ionomer, ethylene- (meth) acrylic acid Copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene-propylene copolymer, methylpentene, polybutene, acid-modified polyolefin resin, polyamide resin, polystyrene resin, low crystalline saturated polyester or non-crystalline Crystalline polyester resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), tetrafluoroethylene-ethylene copolymer (ETFE), polytetrafluoroethylene (PTFE) , It can be used a film made of like MXD6. Or the multilayer film which laminated | stacked two or more layers of these films may be sufficient. In the case of a multilayer film, each layer may have the same composition or a different composition.

In the present invention, these resin films may be films formed by any method such as extrusion film formation and inflation film formation. Further, a resin film obtained by coating polyvinylidene chloride called K coat on these films, for example, K coat polypropylene film, K coat nylon film and the like may be used. These may be unstretched films or may be stretched in a uniaxial or biaxial direction. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.
In particular, when applied to a medical packaging container that requires visibility, a polyethylene terephthalate (PET) film excellent in transparency is preferably used.

Of the above films, a film made of a gas barrier resin such as polyvinylidene chloride, polyvinyl alcohol, MXD6 or the like can exhibit good gas barrier properties without further providing a barrier layer.
In the present invention, the thickness of the base material layer may be arbitrary, but is preferably 5 to 300 μm and more preferably 10 to 100 μm from the viewpoint of moldability and transparency.
The film constituting the base material layer may be subjected to pretreatment for improving wettability such as corona treatment, ozone treatment, and frame treatment on the side where the adhesive layer is laminated.

<3> Barrier layer The packaging material of the present invention, in particular, when applied to medical packaging containers for medical products such as pharmaceuticals such as liquids and prefilled syringes containing liquids, in order to prevent weight loss of the contents, Alternatively, a barrier layer is preferably provided in order to prevent deterioration of the contents.
In the present invention, the barrier layer is, for example, a metal foil made of aluminum foil or the like, a vapor deposition film of an inorganic substance or an inorganic oxide, a vapor deposition film having the vapor deposition film on a resin film, or an ethylene-vinyl alcohol copolymer, It may be a layer made of a gas barrier resin such as vinylidene chloride, polyvinyl alcohol, MXD6, or a combination thereof.

  Usually, the thickness of the barrier layer is preferably 0.01 to 500 μm, more preferably 1 to 300 μm from the viewpoint of gas barrier properties and transparency. The barrier layer may be subjected to surface treatment for improving wettability, such as corona treatment, ozone treatment, and flame treatment, on at least one surface thereof.

In order to use it for packaging of medical packaging containers, for example, pharmaceuticals such as liquids and tablets, medical instruments, medical products such as prefilled syringes, etc., it is preferable to have visibility, and it is preferable to use a transparent gas barrier film. In particular, since it exhibits excellent gas barrier properties, transparency, and interlayer adhesion strength, in the present invention, an inorganic oxide vapor-deposited film or an inorganic oxide vapor-deposited film formed by providing the vapor-deposited film on a plastic film is provided. Particularly preferably used.
In the present invention, being transparent means that it is necessary to have the transparency necessary for the application, and includes colorless or colored and transparent, particularly when used as a medical packaging container. For example, the average light transmittance in the visible light region of 380 to 780 nm is 70% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and the air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

The gas barrier film used in the present invention can be appropriately selected by those skilled in the art to exhibit a necessary level of gas barrier properties depending on the application. For use as a medical packaging container, for example, the oxygen permeability is 0.5 cc / m ² / day · atm or less, more preferably 0.3 cc / m ² / day · atm or less, and the water vapor permeability is It is 0.3 g / m ² / day or less, more preferably 0.1 g / m ² / day or less. In this application, the oxygen transmission rate is a condition of a temperature of 23 ° C. and a humidity of 90% RH using an oxygen gas transmission rate measuring device (OX-TRAN 2/20 manufactured by MOCON) in accordance with the JIS K7126 isobaric method. It is a value measured by. Further, the water vapor transmission rate is measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON) in accordance with JIS K7129 B method. Value.

A vapor deposition film and a vapor deposition film are demonstrated in detail. As the plastic film for forming the vapor deposition film, a plastic film that has excellent chemical or physical strength, can withstand the conditions for forming the vapor deposition film, etc., and can be well maintained without impairing the characteristics of the vapor deposition film is used. be able to.
As such a plastic film, for example, a polyolefin film such as polypropylene or polyethylene, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate, a film or sheet made of various resins such as a polyamide film or a polyimide film is used. can do.

  Plastic film is treated with corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemical treatment, etc. as necessary before providing a vapor deposition film. Etc. can be arbitrarily applied. In addition, the surface pretreatment is performed as a method for improving the adhesion between the plastic film and the vapor deposition film. As a method for improving the adhesion, for example, the surface of the plastic film is preliminarily formed. In addition, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, or the like can be arbitrarily formed.

The material for forming the vapor deposition film may be an inorganic oxide having transparency and gas barrier properties such as oxygen and water vapor, such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, Although oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide are used, aluminum oxide and silicon oxide are particularly preferably used from the viewpoint of gas barrier properties and production efficiency.

  As a method for forming a deposited film, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method and ion plating method, plasma chemical vapor deposition method, thermal chemical vapor deposition method, etc. And film forming methods such as chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

Moreover, the vapor deposition film may consist of a single layer formed by a single vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on a plastic film by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.
The layer thickness of the deposited film can be appropriately set within the range of 1 to 200 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm as the thickness of the entire layer. For example, if it exceeds 200 nm, the flexibility is lowered, and there is a possibility that the deposited film may be cracked by an external force such as bending or pulling after film formation, transparency may be lowered, and the stress of the material itself may be reduced. It becomes undesirably large and colored. On the other hand, when the thickness of the deposited film is less than 1 nm, the transparency is good, but it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Hereinafter, as a preferred embodiment of the present invention, a deposited film of silicon oxide will be described in more detail. The vapor-deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide.

As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, at the interface with the plastic film, the plastic film and the silicon oxide vapor deposition film The tight adhesion is strong.
When forming a silicon oxide vapor-deposited film containing carbon as described above, the organic silicon compound used as a raw material is 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO) , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.

In the present invention, by further providing a gas barrier coating film as described below on the vapor deposition film, not only a further excellent gas barrier property can be obtained, but also a close adhesion with an adhesive layer described later is enhanced. .
In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.
The alkoxide used in the gas barrier composition has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M is a metal An atom is represented, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, n + m represents the valence of M.) At least 1 type or more alkoxide represented by this can be mentioned. .
As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.

In the present invention, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.

  Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 weight part with respect to 100 weight part of total amounts of said alkoxide. In the above, if it exceeds 500 parts by weight, the formed gas barrier coating film becomes more brittle and its weather resistance and the like are also unfavorable.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1000), Kuraray Poval LM-20SO manufactured by the same company (degree of saponification = 40%, degree of polymerization = 2000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization) Degree = 1400) and Gohsenol NH-18 (degree of saponification = 98-99%, degree of polymerization = 1700) and the like can be used.

In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

  In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.
The gas barrier coating film is formed by applying the gas barrier composition on the vapor deposition film, and is 10 to 10 seconds at a temperature of 20 to 200 ° C., preferably 140 ° C. or more and below the melting point of the plastic film constituting the base material layer. It can be formed by heat treatment for minutes.

Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.
Further, regarding the gas barrier composition, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

When the gas barrier composition is applied onto the vapor deposition film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed.
Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the deposited film, the tight adhesion between the deposited film and the gas barrier coating film is improved. .

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

In the present invention, the vapor deposition film and the gas barrier coating film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved, synergistically. Due to the effect, a better gas barrier property can be exhibited.
In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, it is possible to form a gas barrier coating film having a dry film thickness of 0.01 to 100 μm, preferably 0.1 to 50 μm. If the dry film thickness exceeds 100 μm, cracks may occur, which is not preferable.
In the present invention, in order to obtain a higher gas barrier property, after providing a gas barrier coating film, a vapor deposition film and a gas barrier coating film are alternately laminated in this order one or more times. Preferably, the gas barrier coating film may be formed as an outermost layer to form a transparent gas barrier film.

<4> Adhesive layer In the present invention, the adhesive layer located between the base material layer or barrier layer and the heat-sealable resin layer is an alkene- (meth) acrylate-unsaturated carboxylic acid ternary copolymer. An adhesive resin composition containing a polymer (hereinafter referred to as “adhesive resin composition of the present invention”). The adhesive resin composition of the present invention exhibits high interlayer adhesive strength with these by being laminated on a base material layer or a barrier layer by an extrusion coating method. Here, the base material layer or the barrier layer may be made of any of the above-described materials, for example, a vapor film or a film made of various gas barrier resins.
In particular, by extruding the adhesive resin composition of the present invention onto the surface comprising a vapor-deposited film of inorganic oxide or the above-mentioned surface comprising a gas barrier coating film, extremely high interlayer adhesion strength is exhibited, and The high interlayer adhesion strength is maintained even after the heat sterilization treatment.

Since the adhesive resin composition of the present invention has a functional group such as a carboxyl group, it chemically binds to a reactive group on the surface of the base material layer or the barrier layer and the surface of the heat-sealable resin layer. The laminate strength can be improved.
In the present invention, an anchor coat agent layer or the like provided in advance during normal extrusion coating on the base material layer or barrier layer is not necessarily required. Moreover, the adhesive resin composition of this invention does not contain an organic solvent. Therefore, according to this invention, the elution of the residual solvent and low molecular-weight substance originating in an anchor coating agent or an organic solvent can be prevented. Further, there is no problem of a decrease in laminate strength due to deterioration of the adhesive layer over time, and it can be applied to a wide variety of uses. In particular, the adhesive resin composition of the present invention is excellent in heat resistance, can maintain a high laminate strength over a long period of time after being subjected to heat sterilization under high temperature and high pressure, and further has excellent content resistance and content. Since deterioration of the adhesive layer due to erosion of an object can be prevented, it can be suitably used as a medical packaging material, as a packaging container for medical products such as liquid medicines and tablets, medical instruments and prefilled syringes.

The adhesive resin composition of the present invention may be composed of only an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer.
In another embodiment, the adhesive resin composition of the present invention further includes, in addition to the above terpolymer,
If desired, a modifying resin such as a polyolefin-based resin, a polyamide-based resin, a polyester-based resin, an ethylene-vinyl alcohol copolymer, polyvinyl chloride, or polyvinylidene chloride may be included. However, the amount of the unsaturated carboxylic acid component and the amount of the (meth) acrylic acid ester component in the composition are adjusted so as to be within the prescribed ranges described later.

  In addition, the adhesive resin composition of the present invention has, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, Various plastic compounding agents and additives can be added for the purpose of improving and improving the mechanical properties, strength, etc., and the addition amount is from a very small amount to several tens of percent depending on the purpose. , Can be optionally added. As a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment and the like can be used.

In the production of the terpolymer, examples of the alkene serving as a comonomer include ethylene, propylene, butene, isobutene, pentene, hexene, and the like. In particular, α-olefins such as ethylene and propylene are preferably used.
Moreover, (meth) acrylic acid ester used as a comonomer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples include tert-butyl (meth) acrylate, ethyl-2-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and methyl acrylate, ethyl acrylate, and butyl acrylate are preferred, and methyl acrylate is more preferred. It is.

  Examples of the unsaturated carboxylic acid serving as a comonomer include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, and derivatives thereof such as acid anhydrides, esters, amides, imides, and the like. Examples thereof include monomethyl maleate, maleic anhydride, citraconic anhydride, itaconic anhydride and the like. In particular, unsaturated dicarboxylic acid, maleic anhydride and the like can be preferably used. These may be used alone or in a mixture of two or more.

  The ternary copolymer is obtained by graft polymerization or ternary copolymerization of the alkene, (meth) acrylic acid ester, and unsaturated carboxylic acid. The ternary copolymer may contain a comonomer other than the above as long as the object of the present invention is not impaired. For example, an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer resin can be preferably used.

In the present invention, the polymerization reaction can be produced by various conventional methods using a comonomer as a raw material.
For example, a polymer consisting of an alkene is dry blended with an unsaturated carboxylic acid and, if necessary, an organic peroxide and a radical initiator at a predetermined mixing ratio using a Henschel mixer, etc., and the system is purged with nitrogen gas. It is obtained by charging into a kneading machine such as a Banbury mixer, a double screw mixer or the like, and melt-kneading at a temperature of 120 to 300 ° C. for 0.1 to 30 minutes. At the time of the grafting reaction, the reaction can be carried out efficiently by adding a conventional radical generator.

Although it does not specifically limit as a radical generator, For example, hydroperoxides, such as diisopropyl benzene hydroperoxide and 2, 5- dimethyl- 2, 5- di (hydroperoxy) hexane; Di-t-butyl peroxide Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; organic peroxides such as diacyl peroxides such as benzoyl peroxide, or azobisisobutyronitrile An azo compound such as These radical generators may be used alone or as a mixture of two or more. The addition amount of the radical generator is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the comonomer components.

In the present invention, in order to obtain good handling while suppressing hygroscopicity, a suitable blending ratio of each component is a component (residue) derived from a (meth) acrylate ester with respect to the total mass of the adhesive resin composition. ) Is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
Further, the unsaturated carboxylic acid-derived component (residue) is contained in an amount of 0.05 to 3.0% by mass, more preferably 0.05% by mass to less than 1.0% by mass, and the rest is derived from an alkene. It is a component (residue), a modifying resin, an additive, and the like.

When the amount of unsaturated carboxylic acid component in the adhesive resin composition containing the terpolymer of the present invention is more than the above range, the acid content of the laminate increases, so that the hygroscopicity is increased, and foaming occurs during extrusion coating. there's a possibility that. Moreover, since the residual monomer of unsaturated carboxylic acid elutes from an adhesion layer, we are anxious about hygiene. Furthermore, it is inferior to bending resistance. Furthermore, since it is highly corrosive to metals, problems are likely to occur in the manufacturing process.
On the other hand, when the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the transparent gas barrier film or the heat-sealable resin is difficult to occur, which may cause a decrease in interlayer adhesive strength.

  When the content of the (meth) acrylic acid ester-derived component is more than the above range, the resin itself is liable to be liquefied, resulting in poor handling. Moreover, when content of the component derived from (meth) acrylic acid ester is less than the said range, the adhesion | attachment by reaction of an acrylate becomes difficult to generate | occur | produce and the adhesive strength with the layer which consists of polypropylene, PET, etc. falls.

It is preferable that MFR of the adhesive resin composition of this invention is 3-100 g / 10min in 190 degreeC, More preferably, it is 5-20 g / 10min. When the MFR is outside the above range, there is a problem that extrusion becomes difficult.
Moreover, it is preferable that the thickness of the contact bonding layer which consists of adhesive resin compositions is 0.1-200 micrometers, More preferably, it is 1-100 micrometers. When the film thickness is not more than the above range, it is difficult to extrude easily and the adhesive strength is not exhibited. When the film thickness exceeds the range, problems such as adhesive strength are solved, but the packaging material cost increases due to excessive use of the resin.

The adhesion mechanism of the adhesive layer comprising the adhesive resin composition of the present invention includes a mechanism for adhering by the flexibility of the adhesive resin composition, a mechanism for adhering by compatibilization with the resin, the surface of the counterpart substrate and the unsaturated carboxylic acid There are a mechanism for adhering by chemical interaction with the substrate, a mechanism for adhering by chemical interaction of unsaturated carboxylic acid and acrylate to the surface of the counterpart substrate, and a mechanism for adhering by radical generation by extrusion at high temperature.
The adhesive layer made of the adhesive resin composition of the present invention is not necessarily bonded by one bonding mechanism, and is bonded by utilizing at least two or more of the above reactions. For example, for polyethylene and ethylene copolymers, the compatibility mainly due to the alkene moiety contributes to bonding. In addition, the reaction between the polar groups of the unsaturated carboxylic acid and the counterpart substrate contributes to the binding to the vapor deposition film or metal of the gas barrier film. In addition, for a layer made of polypropylene or PET, chemical interaction between the acrylate and the unsaturated carboxylic acid contributes to bonding.

In the present invention, the adhesive layer is a layer obtained by co-extrusion coating in this order on the base material layer or the barrier layer with the layer made of the adhesive resin composition of the present invention and the heat-sealable resin layer. Also good. By laminating the base material layer and the heat-sealable resin layer in this order, that is, through the layer made of the adhesive resin composition of the present invention, high interlayer adhesive strength can be obtained.

<5> Heat-sealable resin layer The heat-sealable resin layer of the present invention is a layer made of a heat-sealable resin that can be melted by heat and fused to each other.
Examples of the heat-sealable resin suitably used in the present invention include polyolefin resins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, and ethylene-vinyl acetate. Polymers, ionomer resins, ethylene- (meth) ethyl acrylate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-propylene copolymers, methylpentene polymers, polyolefin resins such as polyethylene or polypropylene are acrylic Polyolefin resins modified with unsaturated carboxylic acids such as acid, methacrylic acid, maleic anhydride, fumaric acid, etc., ethylene- (meth) acrylate-unsaturated carboxylic acid terpolymer resins, cyclic polyolefin resins, Cyclic olefin copolymer And polyethylene terephthalate (PET), polyacrylonitrile (PAN) 1 kind or resin comprising more like. A film or sheet made of these resins may be used, and the surface thereof may be subjected to corona treatment, flame treatment, ozone treatment or the like as desired.

The thickness of the heat-sealable resin layer is not particularly limited, but is preferably 5 to 500 μm, more preferably 10 to 250 μm. If the thickness is less than 5 μm, a sufficient laminate strength cannot be obtained even if heat sealing is performed, and it does not function as a packaging container. When it is thicker than 500 μm, the cost increases and the film becomes hard and workability deteriorates.
In particular, when applying to applications that have severe restrictions on impurities in medical packaging materials, it is preferable to use polypropylene or polyethylene tube films produced by water-cooled inflation. By producing with a water-cooled inflation film, high transparency and hygiene can be obtained.

<6> Intermediate layer and reinforcing layer In the packaging material of the present invention, it is desired to be placed at any position, for example, between the base material layer and the barrier layer, between the barrier layer and the adhesive layer, or outside the base material layer. Accordingly, further layers such as an intermediate layer and a reinforcing layer can be provided.
The intermediate layer and the reinforcing layer may be any functional layer that imparts the desired physical and chemical properties. For example, in order to improve the flexibility, toughness, flexibility and puncture resistance of the laminate, a biaxially stretched nylon film or a layer made of a polyamide resin can be provided as an intermediate layer or a reinforcing layer. Examples of the polyamide resin suitably used here include metaxylidenediadipamide (MXD-6) nylon, 6-nylon, 6,6-nylon, and the like.
The intermediate layer may be a layer having a barrier property, such as a vapor deposition film or a metal foil, in order to further improve the barrier property.

<7> Lamination The packaging material of the present invention is obtained by laminating the base material layer and the heat-sealable resin layer. If desired, a barrier layer or the like may be further provided between the base material layer and the heat-sealable resin layer.
The base material layer or barrier layer and the heat-sealable resin layer are laminated by sandwich lamination via the adhesive resin composition of the present invention.
The sandwich laminate via the adhesive resin composition of the present invention is such that each of the films to be laminated is fed out at a constant speed, and the heated and melted adhesive resin composition of the present invention is extruded into a thin film between the fed films. It is performed by laminating a film using a cooling roll, a pressure roll, or the like.
In another embodiment, the adhesive resin composition of the present invention and the heat-sealable resin may be laminated on the film constituting the base material layer or the barrier layer by a coextrusion coating method.

Since the adhesive resin composition of the present invention exhibits a high bonding force to the laminated surface of the film, it is not necessary to apply an anchor coating agent to the laminated surface in advance. If necessary, the laminated surface of the film may be subjected to surface treatment such as corona treatment in advance.
The extrusion temperature of the adhesive resin composition of the present invention is in the range of 280 to 330 ° C, more preferably 290 to 320 ° C. When the resin temperature is 280 ° C. or lower, generation of radicals in the adhesive layer is difficult to occur, and sufficient interlayer adhesion strength is not exhibited. On the other hand, if the temperature is 330 ° C. or higher, thermal decomposition of the ternary copolymer occurs, so that sufficient interlayer adhesion strength cannot be obtained, which is not preferable.

<8> Medical packaging container The packaging material of the present invention is folded or overlapped so that the heat-sealable resin layer becomes the innermost layer, and the peripheral edge thereof is, for example, a side seal type, a two-side seal type, Three-side seal type, four-side seal type, envelope sticker seal type, jointed sticker seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. Various forms of packaging containers can be manufactured. In particular, the packaging material of the present invention has a high interlayer adhesion strength, and maintains this even after being subjected to a heat sterilization treatment performed under a high temperature and high pressure such as a retort treatment, and further has excellent content resistance and low elution. In order to show the property, it can be suitably used for medical purposes, that is, as a packaging container such as pharmaceuticals and medical instruments such as liquids, tablets and powders, and prefilled syringes.

In order to manufacture the package by filling the contents, after filling the contents from the filling port left without sealing, the filling port is heat-sealed by, for example, a degassing seal or the like and sealed.
In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
As a base material layer, a biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) with a corona treatment on one side is set in the primary paper feeding unit of an extrusion tandem laminating machine, A 50 μm thick linear low density polyethylene (LLDPE) film with a 7 μm thick aluminum foil (1N30 manufactured by Toyo Aluminum Co., Ltd.) set in the secondary paper feeder and corona-treated on one side as a heat-sealable resin layer (Toyobo Co., Ltd. L6100) was set in the tertiary paper feeder.
Next, from the die 1, an adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3% by mass, (Methyl acrylate component amount: 19% by mass) was melt extruded at 310 ° C. to a thickness of 7 μm, and the corona-treated surface of the biaxially stretched PET film and the aluminum foil were laminated by sandwich lamination while performing ozone treatment.
Next, an adhesive resin composition made of ethylene-methyl acrylate-maleic terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) is formed on the aluminum foil surface of the obtained laminated film from the die 2. ) Was melt-extruded to a thickness of 20 μm at 310 ° C., and at the same time, an LLDPE film was fed out from the tertiary paper feeder and laminated by sandwich lamination. The obtained packaging material of the present invention was aged at 55 ° C. for 3 days and used in the test described below.

[Example 2]
Example 1 except that a 70 μm thick unstretched polypropylene (CPP) film (ZK99S manufactured by Toray Film Processing Co., Ltd.) with corona treatment on one side was used as the heat-sealable resin layer instead of the LLDPE film. Thus, the packaging material of the present invention was obtained.

[Example 3]
As a base material layer, a biaxially stretched PET film having a thickness of 12 μm, which is corona-treated on one side, is mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and hexagonal silicon compound, which is an organosilicon compound, is attached to the corona-treated surface. A 200-nm-thick silicon oxide vapor deposition film was provided using methyldisiloxane (HMDSO) as a raw material. Next, plasma treatment was performed on the surface of the deposited film.
On the other hand, according to the composition shown in Table 1 below, the composition a. EVOH (ethylene copolymerization ratio of 29%) in an EVOH solution prepared by dissolving it in a mixed solvent of isopropyl alcohol and ion-exchanged water. A hydrolyzed liquid composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

Next, the plasma-treated surface on the deposited film surface is coated with the gas barrier composition produced above, and heat-treated at 100 ° C. for 30 seconds to form a gas barrier having a thickness of 0.4 g / m ² (dry operation state). An adhesive coating film was formed.
Next, the transparent gas barrier film formed above is set in an extrusion laminating machine, and the adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer is formed on the surface of the gas barrier coating film from a die. The product (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) was melt-extruded to a thickness of 20 μm at 310 ° C., and at the same time, a 50 μm-thick LLDPE film was fed out and laminated by sandwich lamination. The obtained packaging material of the present invention was aged at 55 ° C. for 3 days and used in the test described below.

[Example 4]
Example 3 except that a 70 μm thick unstretched polypropylene (CPP) film (ZK99S manufactured by Toray Film Processing Co., Ltd.) with one side corona-treated is used instead of the LLDPE film as the heat-sealable resin layer. Thus, the packaging material of the present invention was obtained.

[Example 5]
A transparent gas barrier film produced in the same manner as in Example 3 was set in a primary paper feed unit and a tertiary paper feed unit of an extrusion tandem laminating machine, and was produced by water-cooled inflation and crushed into a flat shape ( The crushed thickness (320 μm) was set in the secondary paper feeder.
Next, an adhesive resin composition (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) made of an ethylene-methyl acrylate-maleic acid terpolymer is melted from the die 1 at 310 ° C. to a thickness of 20 μm. The surface of the gas barrier coating film of the extruded transparent gas barrier film and one side of the CPP tube film crushed flatly were laminated by sandwich lamination.
Next, on the non-laminated surface of the CPP tube film in the obtained laminated film, an adhesive resin composition comprising an ethylene-methyl acrylate-maleic acid terpolymer (from Rotema manufactured by Arkema Co., Ltd.) ^(R) 4503) was melt-extruded to a thickness of 20 μm at 310 ° C., and at the same time, a transparent gas barrier film was drawn out from the tertiary paper feeding unit and laminated by sandwich lamination. The obtained tubular packaging material of the present invention was aged at 55 ° C. for 3 days and used in the test described below.

[Example 6]
In the same manner as in Example 5, except that a low-density polyethylene (LDPE) tube film (thickness of crushed body 400 μm) was used instead of the CPP tube film as the heat-sealable resin layer. A packaging material was obtained.

[Example 7]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.), ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02, methyl acrylate) (Adhesive resin composition) diluted 3.75 times with a component amount of 18% by mass to give an unsaturated carboxylic acid component amount of 0.08% by mass and an acrylic acid ester component amount of 19% by mass in the adhesive resin composition. A packaging material of the present invention was obtained in the same manner as in Example 1 except that the product was used.

[Example 8]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4210 manufactured by Arkema Co., Ltd., unsaturated carboxylic acid 3.6% by mass, acrylic ester component amount 4.5) Mass%) is diluted 4.5 times with ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02), the amount of unsaturated carboxylic acid component in the adhesive resin composition is 0.8% by mass, acrylic ester A packaging material of the present invention was obtained in the same manner as in Example 1 except that the adhesive resin composition having a component amount of 15% by mass was used.

[Comparative Example 1]
As a laminating method, instead of melt-extruding an adhesive resin composition composed of ethylene-methyl acrylate-maleic acid terpolymer and laminating by sandwich lamination, a two-component curable urethane adhesive (main agent RU004 / curing agent H1) A packaging material was obtained in the same manner as in Example 3 except that lamination was performed by dry lamination using Rock Paint Co., Ltd.

[Comparative Example 2]
As a laminating method, instead of melt-extruding an adhesive resin composition composed of ethylene-methyl acrylate-maleic acid terpolymer and laminating by sandwich lamination, a two-component curable urethane adhesive (main agent RU004 / curing agent H1) Packaging material was obtained in the same manner as in Example 4 except that lamination was performed by dry lamination using Rock Paint Co., Ltd.

[Evaluation test]
(Interlayer adhesion strength test)
The laminates of Examples 1 to 8 and Comparative Examples 1 to 2 were cut into strips having a width of 15 mm, and the adhesion part between the base material layer and the heat-sealable resin layer was cut using a Tensilon tensile tester according to JISK6854. In a 25 ° C. atmosphere, the film was peeled in the 90 ° direction at a tensile speed of 50 mm / min, and the interlayer adhesion strength (initial) was measured.
For Examples 2, 4, 5 and Comparative Example 2 using a CPP film as the heat-sealable resin layer, after steam sterilization at 121 ° C. for 25 minutes, the interlayer adhesion strength (after heat treatment) was again measured under the same conditions. ) Was measured.
For Examples 1, 3, 6-8 and Comparative Example 1 using an LLDPE film or an LDPE film as the heat-sealable resin layer, after steam sterilization at 105 ° C. for 30 minutes, the interlayer adhesion strength was again obtained under the same conditions. (After heat treatment) was measured.
The results are shown in Table 2 below.

(Dissolution test)
Using the packaging materials of the examples and comparative examples, the heat-sealable resin layers were overlapped and sealed so that the surface area of the inner surface was 1200 cm ² to produce a three-sided bag body. In the case of Examples 5-6, the inner surfaces of the tube films were overlapped with each other and sealed so that the surface area of the inner surface was 1200 cm ² to prepare a three-sided bag body. About the obtained three-way bag body, 200 ml of clean water was enclosed in a test method according to the elution test of the plastic drug container test method of the Japanese Pharmacopoeia, and this pouch was placed at 121 ° C. for 1 hour (Example 2, 4, 5 and Comparative Example 2) or 100 ° C. for 2 hours (Examples 1, 3, 6 and Comparative Example 1). The pouch was opened and the collected test solution was examined for foaming, pH, potassium permanganate reducing substance, ultraviolet absorption spectrum and evaporation residue as follows.

(Bubbles)
5 mL of the test solution was placed in a stoppered test tube having an inner diameter of 15 mm and a length of 200 mm, and vigorously shaken for 3 minutes, and the time until the generated foam disappeared was measured.

(PH)
1 mL of 1 g / L aqueous potassium chloride solution was added to 20 mL each of the test solution and clean water (control), and the pH was measured to determine the difference from the control.

(Potassium permanganate reducing substance)
To 20 mL of the test solution, 20 mL of 0.002 mol / L potassium permanganate solution and 1 mL of dilute sulfuric acid were added and cooled after boiling for 3 minutes. Thereafter, 0.1 g of potassium iodide was added and left for 10 minutes. After standing, it was titrated with 0.001 mol / L sodium thiosulfate solution (indicator: starch reagent). The difference in consumption of 0.002 mol / L potassium permanganate solution relative to the test solution and control (clean water) was determined.

(UV absorption spectrum)
With respect to the test solution and the control (clean water), the maximum absorbance was measured in each of the wavelength of 220 to 240 nm and the wavelength of 241 to 350 nm by the UV-visible absorbance measurement method.

(Evaporation residue)
20 mL of each test solution was evaporated to dryness on a water bath, the residue was dried at 105 ° C. for 1 hour, and its mass was measured.

  The results are shown in Table 3 below. In addition, the standard in a table | surface points out the standard of the elution thing test | inspection of the Japanese Pharmacopoeia plastic drug container test method.

  From the above results, the packaging material of the present invention can be applied to various resin films, vapor-deposited films, and metal foils, and all showed stable and sufficiently high interlayer adhesive strength. Moreover, the interlayer adhesive strength of 5 N / 15 mm or more sufficient for use as a packaging container could be maintained even after heat treatment. Furthermore, components derived from packaging materials such as organic substances did not migrate into the contents, and sufficiently satisfied the elution test standards of the Japanese Pharmacopoeia plastic drug container test method.

1. Base material layer 2. 2. Adhesive layer 3. Heat sealable resin layer Barrier layer

Claims (8)

At least a base material layer, an adhesive layer and a heat-sealable resin layer in this order,
Adhesive layer, alkene - adhesive resin composition layer composed of a terpolymer of an unsaturated carboxylic acid, - (meth) acrylic acid ester
Or an adhesive resin composition layer comprising an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene- (meth) acrylic acid ester,
Or one or more selected from alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymers and polyolefin resins, polyamide resins, polyester resins, polyvinyl chloride, and polyvinylidene chloride. An adhesive resin composition layer made of a modifying resin ( except when polyvinyl alcohol is included) ,
The unsaturated carboxylic acid component amount in the adhesive resin composition is 0.05% by mass to less than 1.0% by mass, the (meth) acrylic acid ester component amount is 5% by mass to 40% by mass,
MFR of this adhesive resin composition is 5-20g / 10min in 190 degreeC, The medical packaging material characterized by the above-mentioned.   The medical packaging material according to claim 1, further comprising a barrier layer between the base material layer and the adhesive layer.   The medical packaging material according to claim 1, wherein the heat-sealable resin layer is a layer made of a polyolefin-based resin.   The medical packaging container which overlaps the medical packaging material of any one of Claims 1-3 so that the heat-sealable resin layers may oppose, and heat-seals the edge part.   The medical packaging container according to claim 4, wherein the interlayer adhesion strength after heat sterilization treatment at 105 ° C for 30 minutes is maintained at 60% or more with respect to the interlayer adhesion strength before heat sterilization treatment. . The medical adhesive according to claim 4 or 5, wherein the interlayer adhesive strength after heat sterilization treatment at 121 ° C for 25 minutes is maintained at 60% or more with respect to the interlayer adhesive strength before heat sterilization treatment. Packaging container.   The medical packaging container according to any one of claims 4 to 6, which satisfies the elution test standard of the Japanese Pharmacopoeia plastic drug container test method.   It is a manufacturing method of the medical packaging material of any one of Claims 1-3, Comprising: A base material layer or a barrier layer, and a heat-sealable resin layer are made into alkene- (meth) acrylic acid ester-non-use. The production method according to the above, wherein lamination is performed by a sandwich lamination method through a molten adhesive resin composition containing a terpolymer of saturated carboxylic acid.

Images