JP2014140973A - Medical packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical packaging material comprising a laminate which is obtained by bonding a gass barrier film and a polyolefin film without using an adhesive agent and is excellent in weatherability without exudation of a foreign matter or a residual solvent or the like.SOLUTION: There is provided a medical packaging material which comprises a laminate obtained by laminating a gas barrier film having ultraviolet absorptivity and a polyolefin fil. The gass barrier film has ultraviolet absorptivity. The medical packaging material has a light transmittance at 380 nm wavelength of 20% or more and a light transmittance at 600 nm wavelength of 60% or more. The gas barrier film and the polyolefin film are bonded without through an adhesive agent.

Description

  The present invention relates to a medical packaging material, and more particularly, to a medical packaging material using a laminate in which a gas barrier film having ultraviolet absorption performance and a polyolefin resin film are bonded without using an adhesive.

  A package in which a film or the like is processed into a bag shape is used. In such a package, a multifunctional film in which various materials are laminated is used as a film to be used in order to develop a desired function depending on the contents to be filled. For example, in order to prevent deterioration of the contents due to ultraviolet rays, etc., a film having an ultraviolet absorption function is used, or in order to prevent the contents from being altered by oxygen, a gas-impermeable film or oxygen absorption is used. A film having a function is used.

  The package is generally performed by processing a long film, but in order to process it into a bag shape, the end portions of the films are overlapped and bonded. As a method of bonding films, a laminate resin (adhesive) is applied to the ends of the films to be bonded, and the films are pressed and sealed, or the two films are overlapped and heated at the ends. In general, a so-called heat sealing process is performed to add and fuse.

  Since heat sealing does not use a laminate resin or the like when bonding the films, the films can be bonded easily and simply. However, the heat sealing process is a method in which the films are partially melted or semi-melted, and the films are bonded to each other, so that different films, for example, a polyolefin film and a polyester film are bonded to each other. It cannot be bonded by heat sealing. In addition, in heat seal processing, it is necessary to use a film made of a resin that can be fused at a relatively low temperature. Therefore, a multilayer film in which a heat sealable resin layer such as polyolefin resin is provided on the outermost surface layer is used. (For example, JP-A-55-107428).

  On the other hand, when films are bonded together by laminating, the components of the laminating resin are appropriately selected according to the type of film to be used (type of resin). For example, when processing into a bag shape by bonding a polyester film and a nylon film, a urethane adhesive has been used (for example, JP-A-52-82594).

  However, in the case of a package made by bonding films made of different materials through a laminate resin, the laminate resin component may gradually elute or volatilize in the package, and the contents may be altered. In the medical field where cleanliness is important, contamination of the contents by the laminate resin may be a problem. In addition, the laminate resin itself may deteriorate due to long-term use of the package, and particularly in exterior applications that are used outdoors, the weather resistance of the laminated package may become a problem. In addition, in the laminating technique using an adhesive, since a resin component diluted in a solvent is generally applied, the solvent remains after laminating to form a final product such as a package. There was a case.

  In order to solve the above problems, Japanese Patent Application Laid-Open No. 2006-306110 discloses a cyclic olefin copolymer between a laminate resin layer and an innermost layer as a laminate film in which a laminate resin (adhesive) hardly dissolves in a package. It has been proposed to intervene layers.

  By the way, surface modification of a material using radiation or an electron beam has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 2003-119293 (Patent Document 3) proposes that a crosslinked composite fluororesin can be obtained by irradiating the fluororesin with radiation. In Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 (Non-patent Document 1), a polytetrafluoroethylene film and a polyimide film are laminated and an electron beam ( In the following, it has been proposed to bond each other by irradiating EB. In Material Transactions Vol.50, No.7 (2009), pp1859-1863 (Non-patent Document 2), the surface of the polycarbonate resin is covered with a nylon film, and an electron beam (hereinafter abbreviated as EB) may be applied from above. A technique for adhering a nylon film to a polycarbonate resin surface has been proposed. Furthermore, the Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531 (Non-patent Document 3) can be bonded to each other by irradiating EB from a nylon film placed on silicone rubber. Is described.

  Conventionally, in order to store photodegradable pharmaceuticals and medical devices for a long period of time, an aluminum laminated film having excellent light shielding properties and gas barrier properties has been used as a medical packaging material (Patent Document 5). However, it is difficult for the packaging material using the aluminum laminated film to distinguish the contents from the outside of the packaging material. For this reason, there is a problem that the packaging material is unsealed for confirmation or the wrong medical package is unsealed, which impairs the preservation of the contents. In recent years, pharmacies are managing a vast number of drugs due to the spread of generic drugs. Therefore, the contents cannot be discriminated, and a problem that is difficult to use has occurred. Therefore, development of the medical packaging body which can make the photodegradation prevention of the content and the visibility ensuring of the content compatible is earnestly desired.

JP-A-55-107428 JP 52-82594 A JP 2003-119293 A JP 2006-306110 A JP-A-10-264290

Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 Material Transactions Vol.50, No. 7 (2009), pp1859-1863 Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531

  The present inventors have now found that even when films made of different materials are bonded to each other, the films can be firmly bonded to each other without using a laminate resin or the like by irradiating the films with an electron beam. . And even if it is a laminate that has been bonded to each other with an adhesive, such as a laminate of a gas barrier film and a polyolefin film having ultraviolet absorption performance, an adhesive is used according to electron beam irradiation. Even if it did not do, the bond was formed between the atom by the side of a gas-barrier film, and the atom by the side of a polyolefin film, and the knowledge that it mutually adhere | attached was acquired. The present invention is based on this finding.

  Accordingly, an object of the present invention is a medical packaging material comprising a laminate in which a gas barrier film having an ultraviolet absorbing performance and a polyolefin film are bonded without using an adhesive, and foreign matter, residual solvent, etc. are oozed out. The object is to provide a medical packaging material which is free from defects and has excellent weather resistance.

  Another object of the present invention is to provide a medical package capable of achieving both prevention of light deterioration of contents and ensuring of visibility of contents.

The medical packaging material according to the present invention is a medical packaging material comprising a laminate in which a gas barrier film having ultraviolet absorption performance and a polyolefin resin film are laminated,
The medical packaging material has a light transmittance at a wavelength of 380 nm of 20% or less, a light transmittance at a wavelength of 600 nm of 60% or more,
The gas barrier film and the polyolefin resin film are bonded without using an adhesive.

  Moreover, as an aspect of the present invention, a bond is formed between atoms in the gas barrier film and atoms in the polyolefin resin film in at least a part of the gas barrier film and the polyolefin resin film. Is preferred.

  As an aspect of the present invention, the gas barrier film is preferably a laminated film including a gas barrier layer and an ultraviolet absorbing layer.

Moreover, as an aspect of the present invention, the laminated film includes a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier provided on the silicon oxide thin film layer. A protective layer,
The laminate is formed by laminating the laminated film and the polyolefin resin film so that the gas barrier protective layer and the polyolefin resin film face each other.
The gas barrier protective layer comprises a film obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane,
In at least a part of the gas barrier protective layer and the polyolefin resin film, a bond is preferably formed between an atom in the gas barrier protective layer and an atom in the polyolefin resin film.

  Further, as an aspect of the present invention, between the atoms in the polyolefin resin film and the atoms in the gas barrier protective layer, through at least one selected from the group consisting of oxygen, nitrogen, and hydroxyl groups It is preferable that a bond is formed.

Further, as an aspect of the present invention, the alkoxysilane is represented by the following general formula:
R _1n Si (OR ₂ ) _m
(In the formula, R ₁ and R ₂ each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Represents the value.)
It is preferable to be represented by

  In one embodiment of the present invention, the water-soluble polymer having a hydroxyl group is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and an ethylene-vinyl alcohol copolymer. It is preferably a seed or a mixture of two or more.

  Moreover, as an aspect of the present invention, the thermoplastic resin film is preferably an ultraviolet absorbing layer.

  Moreover, as an aspect of the present invention, it is preferable that an ultraviolet absorbing layer is further included between the thermoplastic resin film and the thin film layer and / or on the surface opposite to the thin film layer of the thermoplastic resin film.

  As an aspect of the present invention, it is preferable that the ultraviolet absorbing layer comprises at least one selected from the group consisting of a benzophenone ultraviolet absorber, a triazine ultraviolet absorber, and a benzotriazole ultraviolet absorber. .

  Moreover, as an aspect of the present invention, it is preferable that the ultraviolet absorbing layer further includes a coloring material.

  Moreover, as an aspect of the present invention, the polyolefin resin film is preferably a polyethylene film or a polypropylene film.

  Moreover, as an aspect of the present invention, the thermoplastic resin film is preferably a polyethylene terephthalate film.

Moreover, the method for producing a medical packaging material as another aspect of the present invention comprises a laminate in which a gas barrier film having ultraviolet absorption performance and a polyolefin resin film are laminated, and has a light transmittance of 20% at a wavelength of 380 nm. A method for producing a medical packaging material having a light transmittance of 60% or more at a wavelength of 600 nm, comprising:
Irradiating at least one surface of the gas barrier film and / or the polyolefin resin film with an electron beam, and bonding the surface irradiated with the electron beam to form a laminate. It is a feature.

  As an aspect of the present invention, the gas barrier film is preferably a laminated film including a gas barrier layer and an ultraviolet absorbing layer.

Further, as an aspect of the present invention, the laminated film is a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier property provided on the silicon oxide thin film layer. Comprising a protective layer and
The gas barrier protective layer surface of the laminated film and / or at least one surface of the polyolefin resin film is irradiated with an electron beam, and the gas barrier protective layer surface irradiated with the electron beam of the laminated film and the polyolefin resin film surface It preferably comprises bonding to form a laminate.

  As an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after the gas barrier film and the polyolefin resin film are overlapped.

  Moreover, as another aspect of the present invention, the bonding is preferably performed by applying pressure, and the bonding is preferably performed by heating.

  Moreover, as an aspect of the present invention, it is preferable to add an ultraviolet absorber to the thermoplastic resin film.

  Moreover, as an aspect of the present invention, it is preferable to further provide an ultraviolet absorbing layer between the thermoplastic resin film and the thin film layer and / or on the surface opposite to the thin film layer of the thermoplastic resin film.

  According to the present invention, at least one or more selected from the group consisting of oxygen, nitrogen, and hydroxyl groups directly between the atoms in the gas barrier film having ultraviolet absorption performance and the atoms in the polyolefin resin film Since the bond is formed via the adhesive, a medical packaging material comprising a laminate in which the laminated film and the polyolefin resin film are firmly bonded can be obtained even if the adhesive is not bonded via an adhesive. As a result, it is possible to realize a medical packaging material that does not exude foreign matter or residual solvent and has excellent weather resistance.

It is the schematic sectional drawing which showed one Embodiment of the laminated body by this invention. It is the schematic sectional drawing which showed one Embodiment of the laminated body by this invention. It is the schematic sectional drawing which showed one Embodiment of the laminated body by this invention. It is the schematic diagram which showed one Embodiment of the manufacturing method of the laminated body by this invention. It is the schematic schematic diagram which expanded a part of manufacturing process. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention.

  The medical packaging material by this invention consists of a laminated body which laminated | stacked the gas barrier film which has an ultraviolet-ray absorption capability, and the polyolefin resin film. First, the laminated body used for this invention is demonstrated.

<Laminate>
Hereinafter, the laminated body used for this invention is demonstrated, referring drawings. As shown in FIG. 1, the laminate 1 has a structure in which a gas barrier film 20 and a polyolefin resin film 10 are laminated without using an adhesive. In the present invention, it is preferable that a bond is formed between an atom in the gas barrier film and an atom in the polyolefin resin film in at least a part of the gas barrier film and the polyolefin resin film.

  As shown in FIG. 2, the laminate 1 includes a gas barrier film 20, a thermoplastic resin film 21, a thin film layer 22 made of silicon oxide provided on at least one surface of the thermoplastic resin film 21, and a silicon oxide thin film layer. The laminated film which consists of the gas-barrier protective layer 23 provided on 22 may be sufficient. Moreover, the laminated body 1 may provide the ultraviolet absorption layer 24 in the surface on the opposite side to the thin film layer 22 of the thermoplastic resin film 21, as shown in FIG.

  According to a preferred embodiment of the present invention, the gas barrier protective layer 23 corresponding to the adhesive surface of the gas barrier film 20 with the polyolefin resin film 10 is coated with a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. It consists of the resulting coating. In the present invention, a bond is formed between the atoms in the gas barrier protective layer and the atoms in the polyolefin resin film on at least a part of the adhesive surface, so that the gas barrier film and the polyolefin resin film are strong. It is glued to. Usually, the surface of the gas barrier protective layer obtained by applying a solution containing a water-soluble polymer having a hydroxyl group such as polyvinyl alcohol and alkoxysilane is hydrophilic, while the surface of the polyolefin resin film is hydrophobic. Therefore, normally, the two cannot be bonded unless an adhesive is used. In the present invention, as will be described later, the surface of the gas barrier protective layer and / or the polyolefin resin film is irradiated with an electron beam to generate radicals, whereby the atoms in the gas barrier protective layer 23 and the polyolefin resin film 10 A bond is formed with the atoms inside, and the gas barrier film 20 and the polyolefin resin film 10 are firmly bonded without using an adhesive. Generation of radicals by electron beam irradiation can be confirmed by identifying free radical species present in the film after electron beam irradiation using an electron spin resonance apparatus (hereinafter also referred to as ESR). it can.

  The fact that bonds are formed between atoms between the gas barrier film and the polyolefin resin film means that an X-ray photoelectron analyzer (hereinafter also referred to as XPS) or a Fourier transform infrared spectrometer (hereinafter also referred to as FTIR). )). For example, before bonding a gas barrier film and a polyolefin resin film, by measuring the surface state of each film by XPS, confirm what atoms exist on the surface of each film before bonding. Then, both films are bonded by electron beam irradiation to form a laminate, and the laminate is forcibly separated to separate it into a gas barrier film and a polyolefin resin film, and the surface state of each film is again measured by XPS. Then, what atoms are present on the surface of each film is confirmed. As a result, by confirming that there are atoms derived from the polyolefin resin film on the gas barrier film side or atoms derived from the gas barrier film on the polyolefin resin film side, a covalent bond is formed between the two films. You can check whether Moreover, you may confirm by observing the surface of the film after peeling using FTIR.

  In addition, the laminate in which the gas barrier film and the polyolefin resin film are bonded by electron beam irradiation is formed from the group consisting of oxygen, nitrogen, and hydroxyl groups between the atoms in the polyolefin resin film and the atoms in the gas barrier protective layer. A bond may be formed through at least one or more selected. In the laminate according to the present invention, the gas barrier film and the polyolefin resin film are bonded to each other by bonding each other's atoms directly or via at least one selected from the group consisting of oxygen, nitrogen, and hydroxyl groups. Therefore, even if it does not use an adhesive at all, it can be set as the laminated body which does not produce peeling.

Hereinafter, the gas barrier film and the polyolefin resin film constituting the laminate used in the present invention will be described.
<Gas barrier film>
The gas barrier film may be a laminated film including a gas barrier layer and an ultraviolet absorbing layer. Although not shown, the gas barrier film 20 may be a laminated film in which the thin film 22 made of silicon oxide and the gas barrier protective layer 23 are provided not only on one surface of the thermoplastic resin film 21 but also on both surfaces thereof. .

  In the gas barrier film 20 used for the laminate, the thin film 21 made of silicon oxide and the gas barrier protective film 23 form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. Adhesion between the thin film 22 made of silicon oxide and the gas barrier protective layer 23 is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

  As the thermoplastic resin film, any plastic film that can support a thin film made of silicon oxide can be used. For example, polyolefin resin such as polyethylene, polypropylene, polybutene, (meth) acrylic film, etc. Resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyethylene Various resin films such as polyester resins such as terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyamide resins such as nylon 6 and nylon 66, and others can be used. . Among these, polyethylene terephthalate (PET) is preferable, and transparent one is more preferable.

  The thermoplastic resin film may be uniaxially or biaxially stretched, and the thickness is preferably about 10 to 200 μm, particularly about 10 to 100 μm. If necessary, the surface may be coated with an anchor coating agent or the like to be subjected to a surface smoothing treatment or the like.

The thin film layer made of silicon oxide is obtained by forming a thin film of silicon oxide represented by the general formula: SiO _x (wherein x represents a number of 0 to 2) on the surface of a thermoplastic resin film. . As the silicon oxide thin film represented by the above general formula, 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 a chemical bond 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. For example, hydrocarbons having a CH 3 site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol can be used. 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, since the content of the above compound is small at the interface with the base film, the vapor deposition of the base film and the silicon oxide is performed. The tight adhesion with the film becomes strong.

  The thickness of the thin film made of silicon oxide is preferably selected and formed, for example, within a range of about 10 to 3000 mm, particularly about 60 to 1000 mm. The thin film made of silicon oxide may be crystalline or amorphous.

  In the present invention, it is desirable that silicon oxide is vapor-deposited so that the total light transmittance after vapor deposition is less than 90% when the total light transmittance of the thermoplastic resin film constituting the gas barrier film is 100%. In addition, when the total light transmittance of the base film is 100%, it is particularly preferable to deposit silicon oxide so that the total light transmittance after deposition is 85% or more and less than 90%. When the total light transmittance after vapor deposition is 90% or more after vapor deposition, although the transparency is sufficient, the gas barrier property, particularly the gas barrier property against water vapor, may not be sufficiently high. Moreover, when the total light transmittance after vapor deposition is less than 85%, although the gas barrier property is excellent, the final transparency may not reach the total light transmittance of the thermoplastic resin film.

  Next, a method for forming a thin film made of silicon oxide on a thermoplastic resin film will be described. As a method for forming a thin film of silicon oxide, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or a plasma chemical vapor deposition method, Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a thermal chemical vapor deposition method and a photochemical vapor deposition method. In addition, when manufacturing the film which consists of a transparent laminated body used for the packaging material, a vacuum vapor deposition method is mainly used and a plasma chemical vapor deposition method is also used partially.

  In addition, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition. Moreover, the silicon oxide thin film layer in which the content of the compound as described above decreases from the surface of the deposited silicon oxide film in the depth direction is described in Japanese Patent Application Laid-Open No. 2008-143097 by the applicant. It can be formed by such a method. As a conveyance speed of the thermoplastic resin film used as a base material, about 10-800 m / min, especially about 50-600 m / min are preferable.

  In the present invention, the surface of the silicon oxide thin film formed as described above may be subjected to oxygen plasma treatment. The amount of oxygen introduced for the oxygen plasma treatment varies depending on the size of the vapor deposition apparatus and the like, but is usually about 50 sccm to 2000 sccm, and particularly preferably about 300 sccm to 800 sccm. Here, sccm means the average amount of oxygen introduced (cc) per minute in the standard state (STP: 0 ° C., 1 atm). For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem. The method for forming the silicon oxide thin film on the thermoplastic resin film and the method for subjecting the surface of the silicon oxide thin film to oxygen plasma treatment as desired have been described above. However, these are examples, and the present invention is based on these methods. It is not limited to what was obtained.

  Next, the gas barrier protective layer provided on the silicon oxide thin film formed as described above will be described. The gas barrier protective layer can be formed by coating with a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. Examples of the water-soluble polymer having at least a hydroxyl group include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, an ethylene-vinyl alcohol copolymer, and the like. Polyvinyl alcohol is preferred. These resins may be commercially available. For example, as an ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used. Also, as polyvinyl alcohol, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%) manufactured by the same company. Degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

As alkoxysilane, the general formula:
R _1n Si (OR ₂ ) _m
(In the formula, R ₁ and R ₂ each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Can be suitably used. In the above formula, specific examples of the organic group represented by R ₁ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group. , T-butyl group, n-hexyl group, n-octyl group, and other alkyl groups. Specific examples of the alkoxysilane include, for example, tetramethoxysilane: 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 or the like can be used.

  By mixing the above-mentioned water-soluble polymer and alkoxysilane, and further applying a solution containing a sol-gel method catalyst, water, and an organic solvent, if desired, on the surface of the silicon oxide thin film, A gas barrier protective layer can be formed. Moreover, in this invention, the composite polymer layer which laminated | stacked two or more said coating films on the silicon oxide thin film can also be formed.

  Moreover, in this invention, a silane coupling agent can be added to said coating liquid for gas barrier property protective layer formation, and the gas barrier property protective layer obtained by this is especially preferable. As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used. In particular, an organoalkoxysilane having an epoxy group is suitable, for example, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of about 1-20 mass parts with respect to 100 mass parts of said alkoxysilane.

  As a coating method of the coating solution for forming the gas barrier protective layer, conventionally known means such as roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like are used. . Although the thickness of the coating film varies depending on the type of the coating solution, the thickness after drying may be in the range of about 0.01 to 100 μm. It is preferable to be set to ˜50 μm.

  As a sol-gel method catalyst for polycondensation with a coating solution, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is suitable, and 0.01 to 1.0 part by weight, particularly about 0.03 part by weight is used per 100 parts by weight of the total amount of alkoxysilane and silane coupling agent. It is preferable to do.

  Moreover, an acid can also be used as a catalyst of a sol-gel method, for example, mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, organic acids, such as an acetic acid and tartaric acid, and others can be used. The amount of the acid used is preferably about 0.001 to 0.05 mol, particularly about 0.01 mol, relative to the total molar amount of alkoxysilane and the alkoxysilane content (for example, silicate moiety) of the silane coupling agent.

  Water contained in the coating solution is added in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, per 1 mol of the total molar amount of the solution alkoxide. Moreover, it is preferable that the polyvinyl alcohol and the ethylene-vinyl alcohol copolymer contained in the coating liquid for forming a gas barrier protective layer are in a state dissolved in a coating liquid containing the above-described alkoxysilane, silane coupling agent, etc. Therefore, an organic solvent may be appropriately selected and added. For example, as the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

  The gas barrier film used in the laminate of the present invention has ultraviolet absorption performance. It suffices that at least one layer constituting the gas barrier film has ultraviolet absorption performance. For example, the thermoplastic resin film may be an ultraviolet absorbing layer, and an ultraviolet absorbing layer may be provided between the thermoplastic resin film and the thin film layer and / or on the surface opposite to the thin film layer of the thermoplastic resin film. Further, it may be included. Moreover, you may further have other layers, such as a thermoplastic resin film, on an ultraviolet absorption layer. When the polyolefin resin film constituting the medical packaging material is used as an inner layer, an ultraviolet absorber from the inner layer (content side) can be obtained by providing a layer containing an ultraviolet absorber outside the gas barrier protective layer. Elution of other elution components can be suppressed.

  The ultraviolet absorbing layer preferably comprises at least one selected from the group consisting of benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and benzotriazole ultraviolet absorbers, and may further contain a colorant. In particular, it is preferable to contain a combination of a benzophenone ultraviolet absorber and a colorant.

  As the benzophenone ultraviolet absorber, a hydroxybenzophenone ultraviolet absorber is preferably used. Examples of hydroxybenzophenone ultraviolet absorbers include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, Examples thereof include at least one selected from the group consisting of 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, and hydroxymethoxybenzophenone sodium sulfonate.

  As the triazine ultraviolet absorber, a hydroxyphenyl triazine ultraviolet absorber is preferably used. As the hydroxyphenyltriazine-based ultraviolet absorber, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2, 4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxy) Propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, and 2- [4-[(2-hydroxy-3) And (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. It is done.

  Examples of the benzotriazole ultraviolet absorber include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- (2H -Benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert- Til-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-) (3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol), and at least selected from the group consisting of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole One type is mentioned.

  As the colorant, a yellow dye and / or a yellow pigment is preferably used. By using a yellow color material, a light beam having a desired specific wavelength (ultraviolet region) can be absorbed. In the present invention, it is particularly preferable to use a yellow pigment from the viewpoint of light resistance.

The content of the UV absorber UV-absorbing layer is preferably 0.5~0.8g / ^{m 2,} and more preferably 0.55~0.8g / ^{m 2.} Moreover, it is preferable that it is 0.1-1 g / m < ² >, and, as for content of the coloring material in an ultraviolet absorption layer, it is more preferable that it is 0.2-1 g / m < ² >.

<Polyolefin resin film>
As the polyolefin resin film constituting the laminate of the present invention, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polymethylpentene and the like alone, or polypropylene and low density polyethylene And a film made of a mixture of polypropylene and high-density polyethylene can be used. Moreover, you may use what made resin the resin which mixed other resin (for example, elastomer etc.) into polyolefin resin. Among the above resin films, polymethylpentene has excellent performance in gas permeability, chemical resistance, oil resistance, and the like. As such a resin film, you may use a commercially available thing, for example, a TPX film (made by Mitsui Chemicals) etc. can be used conveniently. Further, as a resin obtained by adding an elastomer component to a polyolefin resin, for example, Zeras (registered trademark, manufactured by Mitsubishi Chemical Corporation) can be suitably used. Although the thickness of a polyolefin resin film can be suitably determined according to a use application, it is about 20-300 micrometers in general.

  The laminate obtained by laminating and adhering the gas barrier film and the polyolefin resin film as described above does not exude foreign matter or residual solvent even when using the laminate, and has excellent weather resistance. It can be suitably used for a package used in the medical field, for example, a syringe package bag or a package for filling and packaging a powder or granular pharmaceutical product.

<Method for producing laminate>
Next, a method for producing the laminate as described above will be described with reference to the drawings. First, the gas barrier film 20 and the polyolefin resin film 10 described above are prepared (FIG. 4 (1)), and either or both of the two films are irradiated with an electron beam (FIG. 4 ( 2)). As a result, as shown in FIG. 4 (3), only the portions irradiated with the electron beam are bonded to each other.

  In the present invention, it is preferable to press the superimposed films 10 and 20 using a roller 6 or the like as shown in FIG. 5 immediately after irradiating the film with an electron beam. Since the surfaces of the films 10 and 20 are uneven at the micro level as shown in FIG. 5, even if the films are overlapped with each other, they are not completely adhered, and the contact area at the contact interface between the films is small. In this invention, since the contact area in the adhesive surface of both films increases by pressing the films 10 and 20 with the roller 6 etc. immediately after irradiating an electron beam, adhesiveness improves.

  When the laminated body 1 is pressed after the gas barrier film 20 and the polyolefin resin film 20 are overlapped, it is preferable to press both the films 10 and 20 while heating. By pressing while heating, the flexibility of the films 10 and 20 is improved, and the contact area at the interface (adhesion surface) of the films 10 and 20 can be further increased, so that the adhesion is further improved. The heating temperature may be any temperature at which the film can be thermally deformed, although it depends on the type of film to be used. For example, the heating can be performed at a temperature higher than the glass transition temperature of the resin constituting the film. For example, when a gas barrier film based on polyethylene terephthalate and a polyethylene film are overlapped, the heating temperature is 80 to 180 ° C, preferably 130 to 160 ° C. If the heating temperature is too high, the generated radicals are deactivated, and a strong bond cannot be realized. The pressing force (contact pressure) may be increased, and the heating temperature can be lowered by increasing the contact pressure.

  In order to press the laminate 1 in which the gas barrier film 20 and the polyolefin resin film 10 are overlapped, the heat roller 6 or the like can be suitably used as described above. Further, as shown in FIG. 5, the support roller 7 may be placed at a position facing the heat roller 6 so that the stacked film can be pressed between the heat roller 6 and the support roller 7. . In this way, by placing the support roller 7 at a position facing the heat roller 6, the contact between the laminated body (10, 20) and the heat roller 6 is brought close to the line contact, and the heat roller 6 is laminated by heat. Deformation occurring in the body (10, 20) can be minimized.

  FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In the process of laminating and adhering the gas barrier film 20 and the polyolefin resin film 10, each film 10, 20 is guided to the electron beam irradiation position 3 by the guide roller, and after both the films 10, 20 are irradiated with the electron beam 4. The process of pressing the films 10 and 20 with the heat roller 6 is continuously performed. Each film 10, 20 may be supplied in roll form.

  When irradiating each film with the electron beam 4 from the electron beam irradiation apparatus 3, it is preferable to irradiate the electron beam 4 from the film side with a smaller thickness. Since the electron beam has the property that its transmission power increases as the acceleration voltage increases, depending on the thickness of the film, the electron beam may reach the other film when irradiated with the electron beam from one of the film sides. May not arrive. In that case, the electron beam can reach the deep part of the other film by increasing the acceleration voltage of the electron beam, but unnecessary irradiation is performed on the film itself as the electron beam energy increases. It will deteriorate. Therefore, when a thick film and a thin film are laminated and bonded, it is preferable to irradiate an electron beam from the thin film side without increasing the electron beam energy so much. For example, when the thickness of the gas barrier film is 25 μm or less and the thickness of the polyethylene resin film is 50 μm or more, the electron beam is irradiated from the gas barrier film side. By adopting such an electron beam irradiation method, deterioration of the film can be minimized.

  When the films 10 and 20 to be superimposed are both thick, another electron is placed at a position facing the electron beam irradiation device 3 so that an electron beam can be irradiated from both film sides as shown in FIG. A line irradiation device 3 ′ may be provided. According to this aspect, since the irradiation energy of an electron beam can be adjusted according to the thickness of a film, both films can be adhere | attached, without deteriorating a film.

  FIG. 7 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, the electron beam irradiation is performed before the gas barrier film 20 and the polyolefin resin film 10 are overlapped. First, a pair of supplied films (the gas barrier film 20 and the polyolefin resin film 10) are transferred to the film 10 (20) by the electron beam irradiation device 3 (3 ′) before the films 10 and 20 are overlapped. The electron beam 4 (4 ′) is irradiated. In the embodiment shown in FIG. 6, the films 10 and 20 are overlapped so that the surfaces opposite to the electron beam irradiation side of the films 10 and 20 face each other, whereas in the embodiment shown in FIG. 7, The difference is that the films 10 and 20 are overlapped so that the surfaces of the films 10 and 20 on the electron beam irradiation side face each other. Thus, by superimposing the other film 20 on the surface of the film 10 irradiated with the electron beam, the irradiation energy of the electron beam can be made smaller regardless of the thickness of the film. As a result, the film Degradation due to electron beam irradiation can be further reduced.

  Also in the embodiment shown in FIG. 7, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and electrons are respectively applied to the gas barrier film 20 and the polyolefin resin film 10 as in the embodiment shown in FIG. 6. Lines 4 and 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  FIG. 8 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, the gas barrier film 20 and the polyolefin resin film 10 are overlapped and pressed by the heat roller 6 and then irradiated with an electron beam. First, the pair of supplied films 10 and 20 are led to a guide roller and overlapped. Subsequently, both the films 10 and 20 are pressed by the heat roller 6 and the support roller 7, and heating is performed by the heat roller 6. Thereafter, the electron beam irradiation device 3 irradiates the surfaces of the films 10 and 20 with the electron beam 4 so that the films 10 and 20 are continuously bonded. Also in the embodiment shown in FIG. 8, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and the electron beams 4 and 4 are respectively applied to both films 10 and 20 similarly to the embodiment shown in FIGS. 6 and 6. 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  The irradiation energy of the electron beam needs to be appropriately adjusted according to the film thickness and the like as described above. In the present invention, the electron beam is irradiated in an irradiation energy range of about 20 to 750 kV, preferably 25 to 400 kV, and more preferably about 30 to 300 kV. However, the irradiation energy is preferably lower, and 40 to 120 kV. Can do. Thus, by setting it as low irradiation energy, not only deterioration of a film can be suppressed, but since radical generation | occurrence | production of a film surface occurs more efficiently, stronger bond can be implement | achieved. Further, the electron beam irradiation is performed in the range of absorbed dose of 5 to 2000 kGy, preferably 10 to 1000 kGy.

  As such an electron beam irradiation apparatus, conventionally known ones can be used. For example, a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.) or a line irradiation type low energy electron beam irradiation apparatus (EB-ENGINE). , Manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.

  When irradiating with an electron beam, the oxygen concentration is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone, which may adversely affect the apparatus and the environment. In order to reduce the oxygen concentration to 100 ppm or less, the film may be irradiated with an electron beam in a vacuum or in an inert gas atmosphere such as nitrogen or argon. For example, by filling the electron beam irradiation apparatus with nitrogen, A concentration of 100 ppm or less can be achieved.

  The laminate obtained by laminating the gas barrier film and the polyolefin resin film obtained by the above-described adhesion method can realize an adhesive strength equal to or higher than that obtained by using a conventional laminate resin. In addition, since no laminate resin or the like is used, foreign matter and residual solvent do not ooze out when using a laminate, and the weather resistance is excellent.

<Medical packaging materials>
The medical packaging material by this invention consists of an above-described laminated body. The medical packaging material has a light transmittance at a wavelength of 380 nm of 20% or less, preferably 7% or less, more preferably 2% or less. The light transmittance at a wavelength of 600 nm is 60% or more, preferably 70% or more, more preferably 80% or more. Furthermore, the light transmittance at a wavelength of 390 nm is preferably 20% or less, more preferably 7% or less, and further preferably 2% or less. Alternatively, the light transmittance at a wavelength of 450 nm is preferably 20% or less, more preferably 7% or less, and further preferably 2% or less. The medical packaging material satisfies the light transmittance in the above-mentioned range at these specific wavelengths, thereby achieving both the prevention of light deterioration of light-degradable contents such as pharmaceuticals and medical equipment and ensuring the visibility of the contents. Can do.

The medical packaging material has a water vapor permeability of preferably 0.5 g / (m ² · day) or less, more preferably 0.2 g / (m ² · day) or less, and even more preferably 0.1 g. / (M ² · day) or less. The medical packaging material according to the present invention satisfies the water vapor permeability in the above range, so that the water content in the liquid preparation evaporates even during long-term storage of the liquid preparation, and the concentration of the pharmaceutical in the solution rises above a certain standard. Can be prevented.

  It is preferable that the medical packaging material does not include an aluminum metal foil and / or an aluminum deposited film in any layer. This is because when a layer including an aluminum metal foil and / or an aluminum vapor deposition film is provided, the transmittance of visible light is lowered, and the visibility of the contents is deteriorated.

  The medical packaging material may be a packaging bag or a packaging container. In order to obtain a packaging bag or packaging container using the above laminate, a conventionally known method can be employed. For example, two sheets of a laminate are prepared, and the polyolefin resin film faces are opposed to each other and folded, or the two sheets are overlapped, and the peripheral edges are heat-sealed to provide a seal portion to provide a bag. The body can be configured.

  In addition, as the bag making method, two laminated bodies are prepared, the polyolefin resin film faces are folded so that they face each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, Side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, palm-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, other heat seals Various forms of packaging materials can be produced by heat sealing according to the form.

  As other packaging materials, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like is also manufactured using the laminate. be able to. 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. Note that, for example, a spout such as a one-piece type, a two-piece type, or the like, or an opening / closing zipper can be arbitrarily attached to the packaging material as described above.

  Moreover, it is good also as a form of a blister pack by shape | molding a laminated body. For example, it can be processed into a predetermined shape and form using pressure forming, vacuum forming or a combination thereof, plug assist, and the like.

  The packaging material may be sterilized, and as a method of sterilization, for example, a traveling laminate is used, and this is formed into a bag for packaging while manufacturing the packaging bag. In the sterilization filling and packaging method in which the contents are filled and then the filling port filled with the contents is sealed to produce a packaged product, on the upstream side of supplying the laminated material in the sterilization filling and packaging machine, first, the laminate Then, the hydrogen peroxide mist generated by condensing the hydrogen peroxide solution after being heated and vaporized is supplied to the surface of the preheated laminate, and the hydrogen peroxide mist is applied to the surface of the laminate. Next, the laminate contacted with the hydrogen peroxide mist is dried and sterilized, and then the sterilized laminate is used to make and fill the bag as described above in the sterilization filling and packaging machine. After the packaging process, the packaged product It is possible to elephants.

Example 1
<Preparation of gas barrier film>
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was prepared as a thermoplastic resin film. On one surface, a benzophenone ultraviolet absorber (Daiichi Seika Kogyo Co., Ltd .: L-02) and a yellow pigment (Tokyo Ink ( Co., Ltd .: LG-UV series) and a polyether polyurethane adhesive (Daiichi Seika Kogyo Co., Ltd .: main component—Seika Bond A-188, curing agent—Seika Bond C-89 two-component curing type) The ultraviolet absorbing layer was formed by coating. The thickness of the ultraviolet absorbing layer is 3 μm, and the content of the ultraviolet absorber in the ultraviolet absorbing layer is 0.55 g / m ² . The content of the yellow pigment in the ultraviolet absorbing layer was 0.2 g / m ² .

Then, the silicon oxide thin film was formed in the surface on the opposite side to the ultraviolet absorption layer of a thermoplastic resin film so that it might become a film thickness of 20 nm using the vapor deposition apparatus on the following conditions.
Deposition conditions:
Degree of vacuum in the deposition chamber (after introducing oxygen): 2 × 10 ⁻⁴ mbar
Vacuum degree in the winding chamber: 5 × 10 ⁻³ mbar
Electron beam power: 25kW

Next, a hydrolyzed liquid having the following composition II is added to a mixed liquid containing a polyvinyl alcohol solution having the following composition I, isopropyl alcohol and ion-exchanged water, and the mixture is sufficiently stirred to form a coating solution for forming a gas barrier protective layer. And prepared.
Composition I:
Polyvinyl alcohol 2.33 (mass%)
Isopropyl alcohol 2.70 (mass%)
Water 51.75 (mass%)

Composition II (hydrolyzed solution):
Ethyl silicate 16.60 (mass%)
Silane coupling agent 1.66 (mass%)
Isopropyl alcohol 3.90 (mass%)
0.5N hydrochloric acid aqueous solution 0.53 (mass%)
Water 20.53 (mass%)
Total 100.00 (mass%)

  The above coating solution is coated on the silicon oxide thin film by a gravure roll coating method, and then heat-treated at 180 ° C. for 60 seconds to form a gas barrier protective layer having a thickness of 0.2 μm (dry operation state). As a result, a gas barrier film was obtained.

<Polyolefin resin film>
As the polyolefin resin film, a polyethylene film (PE) having a thickness of 40 μm was prepared.

<Production of laminate>
Samples prepared by cutting the prepared gas barrier film and polyolefin resin film into a size of 150 mm × 90 mm were prepared, and an electron beam irradiation device (line irradiation type low energy electron beam irradiation device EES-L-DP01, Hamamatsu Photonics Co., Ltd.). On the sample stage). At this time, the gas barrier film was placed so that the surface on which the gas barrier protective layer was formed was the upper surface. Further, in order to provide a portion where the sample is not irradiated with the electron beam, masking is performed on one end portion of both samples of about 5 to 10 mm.

Next, after purging with nitrogen gas so that the oxygen concentration in the chamber of the electron irradiation apparatus becomes 100 ppm or less, the surface of the sample was irradiated with an electron beam under the following electron beam irradiation conditions.
Acceleration voltage: 60 kV
Absorbed dose: 200kGy
In-device oxygen concentration: 100 ppm or less

  After irradiating the electron beam, the sample was taken out from the apparatus, immediately overlapped so that the electron beam irradiation surface sides of both films faced each other, and both films were bonded together by a thermal laminating method to obtain a laminate.

Comparative Example 1
The gas barrier film and the polyolefin resin film used in Example 1 were replaced with an electron beam irradiation, and a polyether polyurethane adhesive (Daiichi Seika Kogyo Co., Ltd .: main agent-Seikabond A-188, curing agent-Seikabond C) A laminate was prepared in the same manner as in Example 1 except that the two-component curing type (-89) was used and bonded by the dry lamination method.

<Evaluation of adhesive strength of laminate>
The obtained laminate was cut into a strip shape with a width of 15 mm, and a 90 ° peel test was performed at a rate of 50 mm / min using a tensile tester (Tensilon Universal Material Tester RTC-1310A, manufactured by ORIENTEC). went. The evaluation results were as shown in Table 1 below.

<Elution evaluation>
Two laminates of Example 1 and Comparative Example 1 were prepared, the polyolefin resin film surfaces of the laminate were overlapped, and the three sides of the outer peripheral edge were heat sealed to form a three-side-sealed liquid pouch Next, 100 cc of distilled water was injected from the opening, and the opening was heat sealed to form a packaging bag. In this state, it is stored at 80 ° C. for 2 weeks. After storage, distilled water is taken out from the packaging bag, and the residue obtained by concentration and solidification is analyzed from the packaging bag using a pyrolysis GC / MS apparatus. Was evaluated. The evaluation results were as shown in Table 1 below.

Example 2
In the same manner as in Example 1 except that a triazine ultraviolet absorber (containing hydroxytriazine, BASF Japan Ltd .: TINUVIN 477) was added to the ultraviolet absorbing layer instead of the benzophenone ultraviolet absorber and the yellow pigment. A laminate was produced.

Comparative Example 2
A laminate was produced in the same manner as in Example 1 except that the benzophenone-based ultraviolet absorber and the colorant were not added to the ultraviolet absorbing layer.

Comparative Example 3
A laminated body (opaque) was produced in the same manner as in Example 1 except that an aluminum vapor deposition film was provided instead of the silicon oxide thin film.

  About the medical packaging material which consists of the laminated body produced in Examples 1-2 and Comparative Examples 2-3, each evaluation of light transmittance, water vapor permeability, the color difference after a storage test, and visibility was performed.

<Measurement of light transmittance>
About the medical packaging material, the light transmittance in each wavelength of 380 nm, 390 nm, 450 nm, and 600 nm was measured. The light transmittance was measured using UV-2400PC (manufactured by Shimadzu Corporation) in accordance with JIS-K7105.

<Measurement of water vapor transmission rate>
The water vapor transmission rate of the medical packaging material was measured. The water vapor transmission rate was measured using PERMATRAN-W (manufactured by Mocon) in accordance with “moisture permeability test method” (conditions: 40 ° C., 90% RH) of JIS standard Z-0208 or 0222.

<Measurement of color difference after storage test>
The medical solution was put into the medical packaging material and stored for 14 days at 20 cm directly under the chemical lamp. Thereafter, the chemical solution in the chemical solution container is taken out and the difference in absorbance at all wavelengths in the visible light region (value after storage-value immediately before storage) is calculated using a spectrocolorimeter CLR-7100F (manufactured by Shimadzu Corporation). The color difference was measured. The measurement conditions were transmitted light and a D65 / 10 degree field of view. Further, physiological saline was used for standard calibration.

<Evaluation of visibility>
Medicines were packaged using medical packaging materials. About the pharmaceutical after packaging, the visibility of the contents was judged visually. The evaluation criteria are as follows.
Evaluation criteria : ○: The contents could be discriminated.
-X: The contents could not be identified.

The results of the above evaluation are shown in Table 2. The medical packaging material according to the present invention has excellent visible light permeability and water vapor barrier properties while sufficiently blocking ultraviolet rays. Moreover, it was possible to achieve both prevention of light deterioration of the contents and ensuring of the visibility of the contents.

DESCRIPTION OF SYMBOLS 1 Laminate 10 Polyolefin resin film 20 Gas barrier film 21 Thermoplastic resin film 22 Thin film layer made of silicon oxide 23 Gas barrier protective layer 24 Ultraviolet absorbing layer 3, 3 ′ Electron beam irradiation device 4, 4 ′ Electron beam 5 Film substrate Contact interface 6 Heat roller 7 Support roller

Claims (21)

A medical packaging material consisting of a laminate of a gas barrier film having ultraviolet absorption performance and a polyolefin resin film,
The medical packaging material has a light transmittance at a wavelength of 380 nm of 20% or less, a light transmittance at a wavelength of 600 nm of 60% or more,
A medical packaging material, wherein the gas barrier film and the polyolefin resin film are bonded without using an adhesive.   The medical use according to claim 1, wherein a bond is formed between an atom in the gas barrier film and an atom in the polyolefin resin film in at least a part of the gas barrier film and the polyolefin resin film. Packaging material.   The medical packaging material according to claim 1 or 2, wherein the gas barrier film is a laminated film comprising a gas barrier layer and an ultraviolet absorbing layer. The laminated film comprises a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the silicon oxide thin film layer. ,
The laminate is formed by laminating the laminated film and the polyolefin resin film so that the gas barrier protective layer and the polyolefin resin film face each other.
The gas barrier protective layer comprises a film obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane,
4. The bond according to claim 3, wherein a bond is formed between an atom in the gas barrier protective layer and an atom in the polyolefin resin film in at least a part of the gas barrier protective layer and the polyolefin resin film. Medical packaging material.   A bond is formed between an atom in the polyolefin resin film and an atom in the gas barrier protective layer via at least one selected from the group consisting of oxygen, nitrogen, and a hydroxyl group. Item 5. A medical packaging material according to Item 4. The alkoxysilane is represented by the following general formula:
R _1n Si (OR ₂ ) _m
(In the formula, R ₁ and R ₂ each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Represents the value.)
The medical packaging material of Claim 4 or 5 represented by these.   The water-soluble polymer having a hydroxyl group is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and an ethylene-vinyl alcohol copolymer, or a mixture of two or more. The medical packaging material according to any one of claims 4 to 6, wherein   The medical packaging material according to any one of claims 4 to 7, wherein the thermoplastic resin film is an ultraviolet absorbing layer.   The ultraviolet absorption layer is further included between the said thermoplastic resin film and the said thin film layer, and / or the surface on the opposite side to the thin film layer of a thermoplastic resin film as described in any one of Claims 4-8. The medical packaging material described.   The said ultraviolet absorption layer contains at least 1 sort (s) selected from the group which consists of a benzophenone type ultraviolet absorber, a triazine type ultraviolet absorber, and a benzotriazole type ultraviolet absorber, Any one of Claims 3-9. Medical packaging material as described in 1.   The medical packaging material according to claim 10, wherein the ultraviolet absorbing layer further comprises a coloring material.   The medical packaging material according to any one of claims 1 to 11, wherein the polyolefin resin film is a polyethylene film or a polypropylene film.   The medical packaging material according to any one of claims 1 to 12, wherein the thermoplastic resin film is a polyethylene terephthalate film. A medical packaging comprising a laminate in which a gas barrier film having ultraviolet absorption performance and a polyolefin resin film are laminated, and the light transmittance at a wavelength of 380 nm is 20% or less and the light transmittance at a wavelength of 600 nm is 60% or more. A method of manufacturing a material comprising:
Irradiating at least one surface of the gas barrier film and / or the polyolefin resin film with an electron beam, and bonding the surface irradiated with the electron beam to form a laminate. Characterized method.   The medical packaging material according to claim 14, wherein the gas barrier film is a laminated film comprising a gas barrier layer and an ultraviolet absorbing layer. The laminated film comprises a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the silicon oxide thin film layer,
The gas barrier protective layer surface of the laminated film and / or at least one surface of the polyolefin resin film is irradiated with an electron beam, and the gas barrier protective layer surface irradiated with the electron beam of the laminated film and the polyolefin resin film surface 16. A method according to claim 14 or 15, comprising gluing to form a laminate.   The method according to any one of claims 14 to 16, wherein the electron beam irradiation is performed before and / or after the gas barrier film and the polyolefin resin film are overlapped.   The method according to any one of claims 14 to 17, wherein the adhesion is performed under pressure.   The method according to any one of claims 14 to 18, wherein the adhesion is performed by heating.   The method according to any one of claims 14 to 19, wherein an ultraviolet absorber is added to the thermoplastic resin film.   21. The ultraviolet absorbing layer is further provided between the thermoplastic resin film and the thin film layer and / or on a surface opposite to the thin film layer of the thermoplastic resin film, according to any one of claims 14 to 20. Medical packaging material.

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