JP2013180426A - Medical packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical packaging material comprising a laminate from which a foreign matter and a residual solvent, etc. do not ooze out and is also excellent in weatherability, wherein the laminate is provided by bonding a laminate film including a gas barrier property protective layer and a polyolefin film without using an adhesive.SOLUTION: A medical packaging material comprises a laminate 1 provided by laminating a laminate film 20 that comprises a base material film 21 and a gas barrier property protective layer 23, and a polyolefin resin film 10. In at least a part of the gas barrier property protective layer 23 of the laminated film 20, and the polyolefin resin film 10, a bond is formed between an atom in the gas barrier property protective layer 23 and an atom in the polyolefin resin film 10 and the gas barrier property protective layer 23 and the polyolefin resin film 10 are bonded without an adhesive.

Description

  The present invention relates to a medical packaging material, and more specifically, a thermoplastic resin film, a laminated film in which a thin film layer made of silicon oxide and a gas barrier protective layer are provided in this order, a polyolefin resin film, and an adhesive. The present invention relates to a medical packaging material using a laminate bonded without intervention.

  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.

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

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 laminated film including a gas barrier protective layer and a polyethylene film, 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 laminated film and the atom by the side of a polyethylene 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 laminated film including a gas barrier protective layer 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.

A medical packaging material according to the present invention 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 protective layer provided on the thin film layer made of silicon oxide. A medical packaging material comprising a laminate in which a laminated film comprising a polyolefin resin film is laminated 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 formed between an atom in the gas barrier protective layer and an atom in the polyolefin resin film, and the gas barrier protective layer and The polyolefin resin film is bonded without using an adhesive.

  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 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.

The medical packaging material production method as another aspect of the present invention 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 the silicon oxide thin film layer. Manufacture a medical packaging material comprising a laminate in which a laminated film comprising a gas barrier protective layer provided thereon and a polyolefin resin film are laminated so that the gas barrier protective layer and the polyolefin resin film face each other. A way to
Gas barrier protective layer surface of a laminated film comprising 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 , And / or at least one surface of the polyolefin resin film is irradiated with an electron beam, and the laminate is formed by adhering the gas barrier protective layer surface irradiated with the electron beam of the laminated film and the polyolefin resin film surface. It is characterized by comprising doing.

  Moreover, as an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after the laminated film and the polyolefin resin film are overlaid.

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

  According to the present invention, a laminate comprising 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. Bonds are formed between the atoms in the film and the atoms in the polyolefin resin film, either directly or through at least one selected from the group consisting of oxygen, nitrogen, and hydroxyl groups. Even if it is not bonded via an agent, a medical packaging material comprising a laminate in which the laminated film and the polyolefin resin film are firmly bonded can be obtained. 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 of 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 laminated | multilayer film and the polyolefin resin film. First, the laminated body used for this invention is demonstrated.

<Laminated body>
Hereinafter, the laminated body used for this invention is demonstrated, referring drawings. As shown in FIG. 1, the laminated body 1 has a structure in which a laminated film 20 and a polyolefin resin film 10 are laminated without using an adhesive. The laminated film 20 includes 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 20, and a gas barrier protective layer 23 provided on the silicon oxide thin film layer 22.

  The gas barrier protective layer 23 corresponding to the adhesion surface of the laminated film 20 to the polyolefin resin film 10 is a coating obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. In the present invention, at least a part of the adhesion surface, a bond is formed between the atoms in the gas barrier protective layer and the atoms in the polyolefin resin film, thereby strengthening the laminated film and the polyolefin resin film. It is glued. 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 laminated 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.

  A bond formed between atoms between the laminated film and the polyolefin resin film is also referred to as 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 the laminated film and the polyolefin resin film, by measuring the surface state of each film by XPS, it is possible to confirm what atoms are present on the surface of each film before bonding. Then, both films were bonded by electron beam irradiation to form a laminate, and the laminate was forcibly separated to separate it into a laminate film and a polyolefin resin film, and again, the surface state of each film was measured by XPS. Check what atoms are present on the surface of each film. As a result, by confirming that there are atoms derived from the polyolefin resin film on the laminated film side or atoms derived from the laminated film on the polyolefin resin film side, is a covalent bond formed between both films? You can check if. Moreover, you may confirm by observing the surface of the film after peeling using FTIR.

  Also, the laminate in which the laminated film and the polyolefin resin film are bonded by electron beam irradiation is selected 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 In some cases, a bond is formed via at least one selected from the above. In the laminate according to the present invention, the laminated film and the polyolefin resin film are bonded by bonding each other's atoms directly or through at least one selected from the group consisting of oxygen, nitrogen, and hydroxyl groups. Therefore, even if no adhesive is used, a laminate that does not peel can be obtained.

Hereinafter, the laminated film and the polyolefin resin film constituting the laminate used in the present invention will be described.
<Laminated film>
As shown in FIG. 1, the laminated film 20 includes 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 gas barrier provided on the silicon oxide thin film layer 22. Protective layer 23 is included. Although not shown, the laminated film 20 may be one 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 laminated film 20 used for the laminated body, 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, when the total light transmittance of the thermoplastic resin film constituting the laminated film is 100%, it is desirable to deposit silicon oxide so that the total light transmittance after deposition is less than 90%. 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 of the base film is 100%. 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. However, if the thickness is 50 μm or more, cracks are likely to occur in the film. 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.

<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.

  Various conventionally known additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, a lubricant, and the like can be appropriately added to the polyolefin resin film as necessary. Conventionally known light stabilizers and ultraviolet absorbers can be used. For example, phenol-based, phosphorus-based, hindered amine-based light absorbers, benzotriazole-based, benzophenone-based, and salicylic acid ester-based ultraviolet absorbers are used. it can.

  The laminated body in which the laminated film and the polyolefin resin film are bonded together as described above does not exude foreign matter or residual solvent even when the laminated body is used, and has excellent weather resistance. It can be suitably used for a packaging body used in the field, for example, a packaging body for filling and packaging a syringe packaging bag or a powder or granular medicine.

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

  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. 3 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. 3, even if the films are overlapped, they are not completely adhered to each other, 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.

  After the laminated film 20 and the polyolefin resin film 20 are overlapped, when the laminated body 1 is pressed, 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 laminated film having a polyethylene terephthalate base material and a polyethylene film are laminated, 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 laminated body 1 which laminated | stacked the laminated | multilayer film 20 and the polyolefin resin film 10, the heat roller 6 etc. can be used conveniently as above mentioned. Further, as shown in FIG. 3, the support roller 7 may be placed at a position facing the heat roller 6 so that the superposed 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. 4 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In the process of laminating and adhering the laminated film 20 and the polyolefin resin film 10, each film 10, 20 is guided to the electron beam irradiation position 3 by a guide roller, and the film 10, 20 is irradiated with the electron beam 4 before being heated. The process of pressing the films 10 and 20 with the 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 laminated 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 laminated 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. 5 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 laminated film 20 and the polyolefin resin film 10 are overlapped. First, a pair of supplied films (laminated film 20 and polyolefin resin film 10) are transferred to film 10 (20) by electron beam irradiation device 3 (3 ′) before both films 10 and 20 are overlapped. The electron beam 4 (4 ′) is irradiated. In the embodiment shown in FIG. 4, 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. 5, 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. 5, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and in the same manner as in the embodiment shown in FIG. 4, an electron beam is supplied to each of the laminated film 20 and the polyolefin resin film 10. 4,4 ′ may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In this embodiment, the laminated 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. In the embodiment shown in FIG. 6, 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 in the same manner as the embodiment shown in FIGS. 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, a conventionally known apparatus can be used. For example, 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 laminate 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 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.

<Preparation of laminated film>
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and a silicon oxide thin film was formed on one surface of the film so as to have a film thickness of 20 nm using a vapor deposition apparatus under 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). Thus, a laminated film was obtained.

<Polyolefin resin film>
Moreover, the film formed into 70 micrometers in thickness was prepared using the polypropylene resin (Zeras (trademark) 7025, Mitsubishi Chemical Corporation make) which added the elastomer as a polyolefin resin film.

Example 1
<Production of laminate>
Samples prepared by cutting the prepared laminated 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, manufactured by Hamamatsu Photonics Co., Ltd.). ) On the sample stage. Under the present circumstances, the laminated | multilayer film was mounted so that the surface in which the gas barrier property protective layer was formed may become an 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.
Voltage: 40 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 laminated film and polyolefin resin film used in Example 1 were laminated in the same manner as in Example 1 except that they were bonded together by a dry laminating method using a urethane-based adhesive having the following composition instead of electron beam irradiation. The body was made.

<Urethane adhesive composition>
Main agent: RU0004 (Rock Paint)
Hardener: H-1 (manufactured by Rock Paint)
Mixing ratio: main agent / curing agent = 7.47 / 1 (weight ratio)
Solvent: ethyl acetate

<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.

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

Claims (10)

Laminated film comprising a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, a gas barrier protective layer provided on the silicon oxide thin film layer, and a polyolefin resin film Is a medical packaging material comprising a laminate laminated 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 formed between an atom in the gas barrier protective layer and an atom in the polyolefin resin film, and the gas barrier protective layer and A medical packaging material, wherein the polyolefin resin film is bonded without an adhesive.   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 1. A medical packaging material according to Item 1. 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 1 or 2 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 1 to 3, wherein   The medical packaging material according to any one of claims 1 to 4, 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 5, wherein the thermoplastic resin film is a polyethylene terephthalate film. Laminated film comprising a thermoplastic resin film, a thin film layer made of silicon oxide provided on at least one surface of the thermoplastic resin film, a gas barrier protective layer provided on the silicon oxide thin film layer, and a polyolefin resin film Is a method for producing a medical packaging material comprising a laminate in which the gas barrier protective layer and the polyolefin resin film are laminated so as to face each other,
Gas barrier protective layer surface of a laminated film comprising 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 , And / or at least one surface of the polyolefin resin film is irradiated with an electron beam, and the laminate is formed by adhering the gas barrier protective layer surface irradiated with the electron beam of the laminated film and the polyolefin resin film surface. A method comprising: performing.   The method according to claim 7, wherein electron beam irradiation is performed before and / or after the laminated film and the polyolefin resin film are overlaid.   The method according to claim 7 or 8, wherein the adhesion is performed under pressure.   The method according to claim 7, wherein the adhesion is performed by heating.

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