JP2011105616A - Liner for cataplasm and cataplasm package obtained by combining cataplasm using the liner with cataplasm packing outer package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liner for cataplasm, which maintains a long-term preservation favorably comparable with an aluminum foil package, in a package by sealing and packaging or in an opened part by folding and sealing after opening, has a simple disposal and good user-friendliness, is produced at a low cost and has excellent gas barrier properties and peelability, and a cataplasm package. <P>SOLUTION: The liner for cataplasm is obtained by forming, on a plastic base film, a gas barrier layer-containing gas barrier film, in which a gas barrier coated film layer is laminated or not laminated to a gas barrier continuously vapor-deposited film layer of an organosilicon oxide containing an organic component, and forming a peelable continuously vapor-deposited film layer of an organosilicon oxide containing an organic component on the gas barrier layer. The liner for cataplasm is used as a protective film of cataplasm, a light shielding or light-blocking laminated resin film is laminated to a gas barrier film having a gas barrier layer of the similar lamination structure as that of the liner for cataplasm to give a multilayer laminated film for a cataplasm packing outer package. The cataplasm is combined with a packing outer package prepared from the multilayer laminated film for a packing outer package to give the cataplasm package. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention uses a liner having a gas barrier property and a releasability for protecting and preserving a poultice for percutaneously absorbing a drug by containing the drug in an adhesive layer and affixing it to the skin. The present invention relates to a poultice packaging body using a combination of a poultice and a poultice packaging outer package.

  A poultice consists of a base material such as a non-woven fabric or plastic film coated with an adhesive containing a medicinal component such as an anti-inflammatory agent, an analgesic agent, a poultice, and is applied to the skin with the adhesive. A drug is absorbed through the skin to obtain a medicinal effect.

  The cataplasm is composed of a drug, an adhesive polymer material, and an adhesive base containing a large amount of moisture. Therefore, in the current cataplasm, the adhesive is caused by evaporation of moisture, slow release or alteration of the drug. In order to prevent the adhesiveness and medicinal effect of the layer from being lowered, the substrate is coated with the patch, the patch liner for protecting the adhesive layer, and the outer packaging for packaging the patch. The agent is protected and packaged, the performance of the cataplasm is maintained, and the preservability (called long-term preservability) is enhanced.

  In the conventional packaging exterior body, the exterior body for packaging the poultice is provided with a gas barrier property to cope with long-term storage stability. Aluminum foil with excellent gas barrier properties is used as a packaging material for storing poultices, and the packaging material is composed of base material (paper, plastic) / PE / aluminum foil / PE / sealant extrusion. Laminate specification is used.

  However, since the packaging exterior body having the above-described structure includes aluminum foil, the packaging body is not flexible, and cracks may occur due to bending or the like, resulting in a decrease in long-term storage stability. There is also a problem. Moreover, in the said layer structure, since the gas barrier layer, the printing layer, etc. are provided in another base material, the increase in the weight of a packaging material is produced or it is a design high also in terms of cost.

  A pack of packs has a plurality of packs packaged in a single package, and in the sealed packaging state, there was almost no problem in reducing the performance of the patch, but after opening the package outer package When storing, since the opening of the packaging outer package is folded and sealed, the moisture of the poultice will be volatilized, and even for packaging outer bodies using aluminum foil with excellent gas barrier properties, When used on occasions, the adhesion of the cataplasm to the skin and the cooling effect were reduced.

  On the other hand, as a poultice liner, conventionally, the packaging exterior body plays the role of preserving the poultice, so the adhesive surface of the adhesive layer is mainly temporarily used until the poultice is applied to the human body. It is only necessary to cover the adhesive surface as a liner, and it can be easily peeled off from the adhesive surface during use, such as a polyethylene film, a polypropylene film, a polyester film or other plastic film or a release treatment. Exfoliated paper was used.

  Specifically, in order to maintain the stable performance of the cataplasm and enable long-term storage, improvements have been made conventionally. For example, improving the patch material itself, such as the drug constituting the poultice, the adhesive itself and the adhesive layer composed of the drug and the adhesive, development of a long-term stable drug, adhesive material, adhesive layer Attempts have been made to improve the sustained release of drugs from (Patent Document 1). As an improvement of the base material layer that forms the adhesive layer, the moisture and medicinal components of the poultices are not volatilized. Improvements such as protection with a protective material (Patent Documents 2 and 3) have been made.

  As an improvement of the poultice liner, paying attention to the role of temporarily protecting the adhesive surface, ease of use when applying the poultice to the body, that is, how easy and easy it is to peel off the liner from the poultice. In most cases, the adhesive layer is not entangled and wrinkled, and the main focus is on sticking to the body (Patent Document 4). Therefore, the adhesive layer surface cannot be sufficiently sealed as a protective film, and the function of the adhesive layer may be deteriorated. In view of this, there has been a device designed to reduce the decrease in adhesiveness while maintaining the ease of peeling of the liner (Patent Document 5).

  In addition, there are things that pay attention to the peelability, but the main thing is to improve the commonly used silicone release agent with good peelability (Patent Document 6). When used for medical purposes, it is usually sterilized, and sterilization such as autoclave and radiation is performed, making it difficult for the release sheet to peel off from the adhesive layer and causing heavy peeling. However, it was insufficient from the viewpoint of improvement from the viewpoint of focusing on the releasability, chemical resistance, and gas barrier properties required as a liner in a special field dealing with chemicals called poultices.

  The packaging outer package using aluminum foil with excellent gas barrier properties will not be a big problem before opening, but after opening, the packaging outer package will deteriorate in a short time due to volatilization from the opening etc. As a result, the cataplasm was difficult to store for a long time. Therefore, a rail fastener is provided in the opening so that it can be sealed. However, since the rail fastener structure is specially provided, the manufacturing becomes complicated and the cost is increased.

  At present, problems such as a drop in the performance of cataplasms due to medicinal ingredients and volatilization of moisture, and a decrease in long-term storage stability occur. In fact, it is impossible to wrap a large number of small poultices in a single packaging outer package, because even if a large number of poultices are packaged and sold in one package, the effect is lost. There was a limit to reducing the size and capacity of the cataplasm.

  In this way, in the poultice, it is easy to peel off at the time of use, and in order to maintain the long-term storage stability, each of the poultice liner and the packaging exterior body individually meets the requirements. The current situation is that the performance can be satisfied, and the problems that can be solved by each of the packaging outer package, the cataplasma liner, and the base material are limited, and the solutions are individually supported. In general, there is no patch solution package that can be stored for a long time without any change in moisture and drug components.

Special table 2003-503445 gazette JP 2003-119125 A JP-A-8-217667 JP 2000-219622 A JP 2005-192619 A Japanese Patent Laid-Open No. 3-205699

  The present invention relates to a continuous vapor deposition film of an organic silicon oxide containing a gas barrier organic component formed by a plasma chemical vapor deposition method from a vapor deposition material of a gas composition containing an organic silicon compound on a plastic substrate film. A gas barrier film having a layer and a gas barrier film including a layer structure in which a gas barrier coating film layer is laminated or not laminated on a continuous vapor deposition film of the organosilicon oxide; and a gas composition containing an organosilicon compound It is a poultice liner having a gas barrier property and a releasability by laminating a continuous deposition film layer of an organic silicon oxide containing an organic component having a releasability from a vapor deposition material by a plasma chemical vapor deposition method.

  Moreover, it is a packaging exterior body that does not use an aluminum foil that is used in combination with a cataplasm that improves the storage stability of the cataplasm using the cataplasma liner, and does not use a metal foil such as aluminum, and the cataplasm of the present invention As with the liner, a gas barrier continuous vapor deposition film of an organosilicon oxide is provided on a base film by a plasma chemical vapor deposition method on a base film, and a gas barrier coating layer is laminated thereon or not. A gas barrier film having a gas barrier layer including a layer structure is formed, and the gas barrier film and a sealant film are laminated by a dry laminating method using a urethane adhesive to form a multilayer laminated film for a packaging outer package for a poultice. And the outer packaging body of the present invention and the outer packaging body of the present invention. Poultice package used in combination on.

  As described above, with conventional poultices, attention is paid only to the outer packaging for wrapping the poultice for its long-term storage, and little attention is paid to the release sheet. The package is only seen as a package for preserving the patch in the original packaging decoration and patch, and there is no viewpoint to see the release sheet and the package as a single patch package. It was. For long-term storage, a packaging laminate using an aluminum foil with a gas barrier property is used for the packaging outer package, and there are environmental issues when the packaging is disposed of. When using, the packaging laminate is less flexible and the packaging body becomes stiff, the packaging body is inconvenient, and when the opening is folded and sealed for storage In addition, cracks may occur in the aluminum foil, the sealing performance may be lowered, and the gas barrier property is lowered.

  Therefore, the use of metal foil such as aluminum foil was eliminated to facilitate disposal, and the packaging laminate was required to be made into a plastic film, and the packaging was formed from a multilayer laminated film for packaging outer packaging that was made into a plastic film. Even in this case, it is possible to suppress the deterioration of gas barrier properties due to plastic film, to exhibit the gas barrier properties, and to maintain the long-term storage stability of the poultices without providing special sealing means to improve the sealing properties. The body is sought.

  Furthermore, in a plasticized packaging body, it can be used in combination with a packaging exterior body so that it can exhibit long-term storage and comparable performance after opening with a conventional packaging body using aluminum foil. In addition, it is required to develop a catalyzer liner that can maintain and improve long-term storage stability when used together with the packaging exterior body, and is inferior in peelability, transfer of release agent, and free from contamination. .

Therefore, the object of the present invention is to provide a conventional aluminum film in a hermetically packaged package or in a folded seal of an unsealed portion after opening, even if a plastic film is used or no special sealing means such as a rail fastener is provided. Compared with packaging using foil packaging laminates, it can maintain long-term storage stability, and is easy to use, easy to use, and can be manufactured at low cost. Another object of the present invention is to provide a poultice packaging body comprising a poultice liner excellent in gas barrier properties and peelability and a packaging exterior body used in combination with a cataplasm using the liner.

  In the present invention, in order to solve the above-mentioned problems or to achieve the object, the poultice liner is formed of a gas of an organosilicon compound by a plasma chemical vapor deposition method (hereinafter sometimes referred to as a plasma CVD method or simply a CVD method). A gas barrier continuous vapor deposition film of organic silicon oxide formed from the composition and a peelable continuous vapor deposition film of organic silicon oxide. First, organic silicon oxide is formed on a plastic substrate film by plasma CVD. A gas barrier film having a gas barrier layer on which a gas barrier coating film layer is formed or a gas barrier coating layer is laminated or not laminated thereon, and an organic silicon oxide having releasability on the gas barrier layer The continuous vapor deposition film layer is formed.

  In addition, a patch preparation package for solving the above-mentioned problems of the present invention or for achieving the object is a laminate film including the gas barrier film of the patch agent liner of the present invention as a common gas barrier laminate structure. Adopted as a gas barrier film for an agent packaging outer package, and further, a light-shielding plastic film is laminated on the gas barrier film to form a multilayer laminated film for a poultice packaging outer package, and the packaging produced from the multilayer laminated film for the packaging outer package It is a cataplasm package formed by inserting an armor body and a cataplasm using the cataplasma liner of the present invention as a protective film, and sealingly sealing the opening.

  In the present invention, more specifically, on the surface of a plastic substrate film such as polyester constituting the gas barrier film of the poultice liner and the poultice packaging exterior body, vapor deposition monomer gas of organosilicon compound, oxygen, A gas composition composed of a carrier gas is attached and formed by chemically bonding a continuous vapor-deposited film of an organic silicon oxide containing an organic component under a condition where the oxygen ratio is high. Well, it is characterized in that it is formed by laminating a gas barrier continuous vapor deposition film of an organic silicon oxide that has excellent gas barrier properties and suppresses the influence of a drug on a plastic substrate film. Gas group containing organosilicon compound by plasma CVD method on gas barrier continuous vapor deposition film layer of organosilicon oxide containing components Depositing a peelable continuous deposited film of an organic silicon oxide things the oxygen ratio contains organic components in low conditions, and is characterized in that formation.

  The liner of the present invention forms a gas barrier continuous vapor deposition film layer of an organic silicon oxide containing an organic component and a peelable continuous vapor deposition film layer of an organic silicon oxide containing an organic component by plasma enhanced chemical vapor deposition. A gas barrier continuous vapor deposition film of an organic silicon oxide is formed on a plastic substrate film to form a continuous vapor deposition film layer of an organic silicon oxide having a sufficient thickness, or a different organic silicon oxide A gas barrier film having a gas barrier layer with or without a vapor-deposited thin film layer or gas barrier coating layer, and a peelable continuous vapor-deposited film of organosilicon oxide formed on the gas barrier layer side of the gas barrier film , There is no need to limit the plastic material that constitutes the plastic substrate film, even if an inexpensive material is used, the adhesion between layers is good, there is no delamination, It can be a poultice liner without contamination poultice surface by the transfer and release agents duck gas barrier properties and peelability good and release agent.

  More specifically, in the present invention, since the continuous vapor deposition film is formed by the plasma CVD method, the plastic base film and the organic silicon oxide continuous vapor deposition film layer form a chemical bond. The silicon oxide gas barrier layer and the interlayer between the gas barrier layer and the peelable layer are extremely tightly adhered and hardly peeled from each other, and the peelable layer does not transfer to the adhesive layer.

  Further, in the present invention, organic components such as a compound having a C—H bond or a Si—C bond, an organic silicon compound that is a monomer of a deposition raw material, or a derivative thereof are chemically contained in the continuous deposited film of the organic silicon oxide. As a result of this organic component being cross-linked at the layer interface, the organic silicon oxide continuous vapor-deposited film has a gas barrier property and excellent resistance to chemicals. The migration of the drug from the adhesive layer can be suppressed, the volatilization of the drug and water can be suppressed, and the function as a poultice can be maintained without changing the moisture and drug components of the poultice over a long period of time.

This catalyzer liner can easily change the properties of the organic silicon compound continuous vapor deposition film by controlling the oxygen ratio of the gas composition containing the organic silicon compound, and the organic silicon oxide continuous vapor deposition film. Because it is flexible, it can be easily pressed and applied to the affected skin area when peeling the liner, and has good peelability.
In addition, the gas barrier property and the peelable layer are formed of a continuous vapor deposition film of organosilicon oxide, and the film thickness is thin, the film thickness can be controlled accurately, and the organic silicon oxide continuous vapor deposition film has excellent uniformity. In addition, a uniform gas barrier property and peelable layer can be obtained.

  The packaging exterior body of the present invention employs a gas barrier laminated structure including basically the same layer structure as the gas barrier film of the cataplasma liner for the gas barrier film, and further laminates a light-shielding plastic film on the gas barrier film. A multi-layer laminated film for a packaging exterior body, and since it is produced from the multilayer laminated film for a packaging exterior body, the poultice with the poultice liner of the present invention as a protective film is inserted into the produced packaging exterior body, By using a patch preparation package that is formed by hermetically sealing the opening, a patch agent liner with excellent gas barrier properties prevents moisture from the patch, lowers adhesiveness due to volatilization of the drug, and lowers the efficacy of the drug. It is used as a poultice packaging that guarantees that there is no layer transfer, peelability does not deteriorate, and ease of peeling can be maintained for a long time. It is possible.

  In addition, the packaging outer body of the present invention has a sufficient gas barrier property despite the fact that no aluminum foil is used, and is excellent in gas barrier properties comparable to conventional ones due to the synergistic effect of the liner and the outer body. A poultice pack can be formed. In addition, since the packaging outer package is formed with a flexible gas barrier layer of an organic silicon oxide vapor deposition film layer formed by plasma CVD, there is also the flexibility of the multilayer laminated film for packaging outer packaging, and the opening is bent. When sealing, it is easy to bend without cracks, can maintain its sealing property, has excellent long-term storage stability, and is excellent in waste disposal after use because it does not use aluminum foil.

  And by firmly suppressing the volatilization of moisture and medicinal components from individual poultices as in the present invention, the original medicinal function as a poultice can be maintained for a long time, and wrinkles do not occur as a package, It is easy to bend, does not form cracks, is easy to handle, has excellent functionality such as decorativeness, and is easy to dispose of after use. It can be a package that exhibits long-term storage and is easy to dispose of, and can be used as a substitute for a poultice package that uses aluminum foil.

It is a schematic sectional drawing of an example of the layer structure of the gas barrier releasable patch agent liner in this invention. It is a schematic sectional drawing of other examples of the layer composition of the gas barrier releasable poultice liner which added the gas barrier paint film layer in the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view of an example of a layer structure of a multilayer laminated film for a poultice packaging outer package used for producing a cataplasm packaging outer package used in combination with a liner in the present invention. It is a schematic sectional view of an example of a three-sided seal type bag-shaped exterior body using the multilayer laminated film for a cataplasm packaging exterior body of the present invention.

The present invention will be described in detail below with reference to the drawings.
An example of the layer configuration of a cataplasm in the present invention (hereinafter sometimes simply referred to as “liner”) and a packaging outer package for packaging cataplasm using the liner in the present invention as a protective film, This will be described with reference to the drawings.

  1 and 2 are schematic cross-sectional views of examples of the layer structure of the cataplasma liner (A) in the present invention. FIG. 3 shows an example of the layer structure of a multilayer laminated film for a poultice packaging outer package used for producing a cataplasm packaging outer package used in combination with the gas barrier and peelable catapult liner (A) in the present invention. It is a schematic sectional drawing. FIG. 4 is a schematic cross-sectional view of an example of a three-sided seal-type bag-shaped exterior body using the multilayer laminated film for a poultice packaging exterior body of the present invention.

  In addition, in this invention, a film means all the cases of a sheet | seat, a film, a film-form thing, or a sheet-form thing, and does not give a special meaning.

[Structure of poultice liner and package exterior]
As the cataplasma liner (A) in the present invention, as shown in FIG. 1, an organic component is formed on one side of a plastic substrate film (1) made of a polyester film or the like by a plasma CVD method with or without an easy adhesion layer. A gas barrier coating film layer (2) of an organic silicon oxide containing, and a gas barrier coating film layer (4) laminated with or without forming a continuous deposition film layer of an organic silicon oxide or the like, or A gas barrier film (A ′) is obtained by forming a gas barrier layer that is not laminated, and a peelable continuous vapor deposition film layer of an organosilicon acid compound containing an organic component on the surface of the gas barrier layer by plasma CVD. It is comprised from what formed (3).

  Moreover, as a multilayer laminated film (B) for producing the packaging exterior body (C) for packaging the cataplasm using the cataplasma liner of this invention, as shown in FIG. 3, it consists of a polyester film etc. On one side of the plastic substrate film (1), a gas barrier continuous vapor deposition film layer (2) of organic silicon oxide and an organic silicon oxide vapor deposition layer are continuously formed by plasma CVD with or without an easy adhesion layer. A gas barrier film (A ′) is obtained by forming a gas barrier layer with or without a vapor deposition film layer and with or without a gas barrier coating layer (4) laminated thereon, and the surface of the gas barrier layer A black resin layer using a light-blocking or light-blocking laminated resin film (20), for example, a first or second white resin layer (21) having a sealant property, using an adhesive such as urethane adhesive 22) is laminated to sandwich the light-shielding or light-shielding laminated resin film (20), and a multilayer laminated film (B) for a poultice packaging outer package is produced. The multilayer laminated film (B) is overlapped so that the two sealant layers face each other, and a sealing portion (30) is formed on the three sides by heat sealing or the like, thereby forming a pack outer packaging body (C).

  The multilayer laminated film of the cataplasma liner or cataplasm packaging outer body of the present invention is obtained by depositing a gas barrier continuous thin film of an organosilicon oxide containing an organic component on one side of a base film made of polyester or the like by a plasma CVD method. The basic structure is a gas barrier film having an arranged layer structure.

  In the packaging outer package of the cataplasma liner or cataplasm of the present invention, the organic film is directly contained in the base film made of polyester or the like so as not to sacrifice the gas barrier property when replacing the laminated film laminated with aluminum vapor deposition or aluminum foil. Using an organic silicon oxide gas barrier continuous vapor deposition film layer or an easy adhesion layer provided with an organic silicon oxide gas barrier continuous vapor deposition film layer containing an organic component, In order to obtain the gas barrier property required as a cataplasma liner or cataplasm packaging outer body on the gas barrier layer of the organic silicon oxide continuous vapor deposition film containing an organic component, a vapor deposition film having a predetermined thickness is formed by a chemical vapor deposition method. An organic silicon oxide containing an organic component formed by plasma CVD is formed by providing a sufficient gas barrier property. When used also as a gas barrier layer is may be one that confers the necessary gas barrier property by forming a deposited film of a plasma CVD method to a sufficient thickness the gas barrier property can be exhibited.

  In the present invention, a gas barrier coating film is further formed, and a multilayer gas barrier layer using a vapor deposition film and a gas barrier coating film in combination with a CVD method is used as compared with the case of using an aluminum foil or the like. It is possible to provide gas barrier properties to the extent that there is no problem as a pack for a poultice.

As described above, the present invention is a poultice liner or a poultice packaging outer package capable of imparting gas barrier properties according to requirements by changing the layer configuration, film thickness, and the like of the gas barrier layer.
In addition, by adopting a composite film structure in which a continuously deposited film of organic silicon oxide containing an organic component is formed by plasma CVD, a gas barrier layer of a plastic substrate film and an organic silicon oxide thin film, organic silicon oxide A multilayer structure having a gas barrier property that hardly causes delamination at an interlayer interface such as a gas barrier layer and a vapor deposition layer or a vapor deposition layer and a gas barrier coating layer of a physical thin film can be obtained.

  The present invention provides a basic layer structure of a gas barrier layer composed of a continuous vapor deposition film layer of an organic silicon oxide containing an organic component, and in a poultice liner, ensures the peelability of the poultice liner, Resistant to medicinal components and solubilizers of the adhesive layer, and can maintain the wet state of the adhesive layer and long-term preservation of the medicinal component in cooperation with the gas barrier layer. In order not to lower the adhesive property, a peelable layer composed of a continuously deposited film layer of an organic silicon oxide containing an organic component is further formed on the surface of the gas barrier layer to form a poultice liner.

  The cataplasm packaging exterior body used in combination with the cataplasma liner of the present invention is required to laminate a laminated resin film excellent in light shielding or light shielding properties through an adhesive layer on the gas barrier layer surface of the gas barrier film. As a substitute for a laminated film in which aluminum vapor deposition or aluminum foil is laminated, since a heat-sealable layer is further laminated to form a multilayer laminated film for a poultice packaging exterior body and manufactured using this multilayer laminated film. It can be used, has light-shielding properties, gas barrier properties, and flexibility, and is excellent in waste disposal suitability and environmental suitability without generating harmful substances during incineration disposal after use. By using in combination with a liner, it is a patch packaging outer package that is inferior in long-term storage after opening.

[Plastic base film]
In the present invention, the plastic base film of the poultice liner is excellent in chemical or physical strength, and withstands conditions for forming an organic silicon oxide vapor-deposited film containing an organic component derived from an organic silicon compound, An organic silicon oxide gas barrier containing an organic component by a plasma CVD method, which is a plastic substrate film that can be satisfactorily maintained without impairing the characteristics of an organic silicon oxide-deposited film containing an organic component There is no particular limitation as long as it is a layer that can form a continuous vapor-deposited film and a peelable film.

  Specific examples of materials that can be used as the plastic base film include polyolefin resins such as polyethylene resins, polypropylene resins, and cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile. Ru-butadiene-styrene acrylonitrile ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene na Examples thereof include various resin films such as polyester resins such as phthalates, polyamide resins, polyaryl phthalate resins, polyurethane resins, and cellulose resins. Among these, from the viewpoint of chemical resistance, heat resistance, mechanical properties, dimensional stability, adhesion, price, etc., in the present invention, a polypropylene resin, polyester resin, or polyamide resin film is particularly preferable. . Moreover, the laminated film of 2 or more layers using 2 or more types of resin as a base material may be sufficient.

  What can be used suitably is a biaxially stretched polyester film, for example. Specific examples include polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polybutylene terephthalate (PBT), and polybutylene naphthalate.

  Plastics such as polyester are treated with organic or inorganic fine particles as a lubricant as necessary in order to improve the film take-up property at the time of film formation and the film transportability when coating with an adhesive, etc. , Lubricity may be imparted. Examples of such fine particles include calcium carbonate, calcium oxide, aluminum oxide, kaolin, organosilicon oxide, zinc oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, urea resin particles, melamine resin particles, and crosslinked silicone resin particles. The

  In addition to fine particles, colorants, antistatic agents, antioxidants, lubricants, catalysts, other resins such as polyethylene, polypropylene, ethylene-propylene polymers, olefinic ionomers, etc. are optional as long as the transparency is not impaired. Can be used.

  In the present invention, since the heat treatment is performed to maintain and improve the dimensional stability of the film, it is particularly preferable to add the antioxidant so that the polyester is not colored during the heat treatment. As the antioxidant, phenol, thio, phosphorus, and the like that are suitable for molding process conditions and contribute to stabilization are preferably used.

  In the present invention, the surface of the plastic substrate film is subjected to a desired surface treatment in advance, if necessary, in order to improve the tight adhesion with the continuously deposited film of the organic silicon oxide constituting the gas barrier layer. Can do. As the surface treatment, for example, pretreatment such as corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals or the like can be performed. .

  As a method for improving the tight adhesion between the base film and the gas barrier continuous vapor deposition film of an organic silicon oxide containing an organic component, a continuous organic silicon oxide containing an organic component formed by a plasma CVD method is used. As long as the tight adhesion between the deposited film and the base film does not deteriorate, for example, an easy-adhesion layer such as a primer coat layer, an undercoat layer, an anchor coat layer, an adhesive layer, or a deposited anchor coat layer is formed. You can also.

  As the pretreatment coating material, for example, a polyester resin, a polyamide resin, a polyurethane resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof may be used. it can.

  The thickness of the plastic substrate film used for the poultice liner is not particularly limited, but is such a thickness that does not affect the handleability, strength, etc., and is usually 10 to 100 μm, more preferably 20 to 50 μm.

The method for producing the film of the present invention is not particularly limited, and it is produced by appropriately adopting conventionally known film or sheet production methods such as extrusion method, cast molding method, T-die method, inflation method and the like. can do. In addition, it is possible to form a multilayer by using a method of forming a multilayer film using two or more kinds of resins, and further by using a method of mixing two or more kinds of resins and forming a film before forming the film. Also good.
Further, for example, a uniaxial or biaxial stretching process may be performed using a tenter method or a tubular method.

[Gas barrier layer and peelable layer of organic silicon oxide containing organic components]
In the present invention, the coating material formed on the plastic substrate film is an organic silicon oxide continuous vapor deposition film containing an organic component formed using a vapor deposition monomer gas such as an organosilicon compound, A vapor-deposited monomer gas such as a silicon compound chemically reacts with an oxygen gas, and the reaction product adheres to one surface of the base film, and the organic silicon oxide containing a dense and flexible organic component. A continuous vapor deposition film layer is formed and used as a gas barrier layer or a peelable layer. In the organic silicon oxide continuous vapor deposition film, a compound having a C—H bond or a Si—C bond, a vapor deposition raw material An organic component such as an organosilicon compound as a monomer or a derivative thereof is contained by a chemical bond or the like. Gas barrier property or peelable layer due to cross-linking of the organic component in the continuously deposited film of the organic silicon oxide containing this organic component (hereinafter sometimes simply referred to as “carbon-containing organic silicon oxide”) at the interface. Can act as

More specifically, the organic silicon oxide continuous vapor deposition film of the present invention is a carbon-containing organic silicon oxide continuous vapor deposition film represented by SiOxCy (where 0 <x ≦ 2.5).
In the peelable layer, x is preferably in the range of 0.3 to 1.5, y is preferably in the range of 1.2 to 2.4, and x is 1.0 to 1.4. More preferably, y is in the range of 1.5 to 2.1.
In the gas barrier layer, x is preferably in the range of 1.3 to 2.5, y is preferably in the range of 0.20 to 1.5, and x is in the range of 1.5 to 2.0. More preferably, y is in the range of 0.70 to 1.30.

In the present invention, the thickness of the gas barrier continuous vapor-deposited film of carbon-containing organic silicon oxide is preferably selected and formed within a range of 5 to 100 nm.
If the thickness is 5 nm or less, the planar density of the deposited film is lowered and the base film is exposed on the surface, and sufficient gas barrier properties cannot be obtained, and a uniform gas barrier layer cannot be obtained. Further, the possibility that the deposited film of the organic silicon oxide is peeled off increases. On the other hand, if it is thicker than 100 nm, the rigidity increases and cracks or the like are likely to occur in the film, which is not preferable. Increasing the thickness more than necessary is related to the formation rate of the deposited film, resulting in a decrease in productivity and high cost.

  In the present invention, the continuous vapor deposition film of carbon-containing organic silicon oxide is specifically prepared by using a monomer gas for vapor deposition of an organic silicon compound as a raw material on one side of a plastic substrate film, and using argon gas or helium gas as a carrier gas. Continuous vapor deposition film of carbon-containing organosilicon oxide by low-temperature plasma chemical vapor deposition using a gas composition containing an inert gas such as oxygen gas and an oxygen supply gas such as oxygen gas Is formed by chemical vapor deposition.

  The organic silicon oxide continuous vapor deposition film is formed by changing the vapor deposition conditions containing an organic component derived from the organic silicon compound to form the organic silicon oxide continuous vapor deposition film, thereby providing a gas barrier property of the organic silicon oxide. It is a continuous vapor deposition film or a peelable continuous vapor deposition film. For example, the oxygen supply gas amount such as oxygen gas to be supplied is increased, the oxidation rate of the organic silicon compound is increased, and a continuous vapor deposition film of carbon-containing organic silicon oxide is formed to form a peelable layer, and the oxygen supply amount Is formed as a gas barrier layer by forming a continuous vapor-deposited film of an organic silicon oxide so that the content of organic components is increased. The base film which has the gas barrier property or peelability of the continuous vapor deposition film | membrane of the carbon containing organosilicon oxide in invention is manufactured.

  In the present invention, the organic silicon oxide continuous vapor deposition film layer may be not only one layer of the organic silicon oxide continuous vapor deposition film layer, but also a multilayer film in which two or more layers thereof are laminated, The material to be used can also be used by 1 type, or 2 or more types of mixtures, and a continuous vapor deposition film layer can also be comprised from the organosilicon oxide which mixed the dissimilar material.

As the organosilicon compound used for forming the carbon-containing organosilicon oxide thin film constituting the gas barrier layer or peelable layer of the present invention, it contains a methyl group or an ethyl group, and Si is the main chain. Monomer materials such as 1,1,3,3-tetramethyldisiloxane (TMDSO), hexamethyldisiloxane (HMDSO), vinyltrimethylsilane, methyltrimethylsilane (MTMOS), hexamethyldisilane, methylsilane, Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethylsilane It can be used b tetrasiloxane like.
The monomer material is an organic silicon compound containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups, any material having an appropriate vapor pressure at room temperature and capable of performing plasma CVD. Such materials may be used.

In the present invention, the compound contained in the continuous vapor deposition film layer of the carbon-containing organic silicon oxide, in particular, contains many compounds having a basic structure of hydrocarbon having CH ₃ sites due to cross-linking at the interface, etc. The organic silicon oxide thin film is preferable because it functions as a gas barrier property of the organosilicon oxide thin film as well as a migration blocking layer for medicinal components.

  In the present invention, as the organosilicon compound, in particular, 1,1,3,3-tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS) or hexamethyldisiloxane (HMDSO) is used as a raw material. It is particularly preferable from the viewpoints of its handleability and characteristics such as water repellency and peelability of the formed organic silicon oxide vapor-deposited film.

[Plasma CVD (Plasma Chemical Vapor Deposition)]
The conditions for introducing methyl groups and / or ethyl groups into the organic silicon oxide by plasma CVD are not only the use of the materials described above, but also monomer materials containing Si atoms and CH ₃ groups and / or C ₂ H ₅ groups. And the composition ratio of the mixed gas containing oxygen gas is 10 parts by weight to 1000 parts by weight of oxygen gas with respect to 100 parts by weight of the monomer material. If the oxygen gas is less than 10 parts by weight, a continuous vapor deposition film of carbon-containing organosilicon oxide cannot be formed. If the oxygen gas exceeds 1000 parts by weight, organic components such as methyl groups and ethyl groups are oxygenated. Reacts with CO ₂ and disappears as H ₂ O, and the continuous vapor-deposited organic silicon oxide film contains no methyl or ethyl groups. A continuous vapor deposition film layer of organic silicon oxide with controlled properties is formed.

Moreover, the thickness of the continuous vapor deposition film of at least 1 nm or more is required. When the thickness of the deposited film is less than 1 nm, it does not exist as a continuous film.
In order to change the film thickness of the organic silicon oxide continuous vapor deposition film layer, the volume rate of the continuous vapor deposition film layer is increased as a condition during vapor deposition, that is, the amount of monomer gas and oxygen gas is increased, and the substrate The film thickness can be increased by slowing the film conveyance speed, and the film thickness can be decreased by decreasing the deposition speed.

In order to form a deposited film of an organic silicon oxide by plasma CVD, it is necessary to introduce oxygen gas in addition to the monomer material to the gas composition. An oxidizing gas such as ozone gas or laughing gas (N ₂ O) can be used instead of oxygen gas, but oxygen gas is most preferable from the viewpoint of film forming efficiency and cost.

In addition to the monomer gas and oxygen gas, the gas (carrier gas) for efficiently introducing the monomer vapor into the vacuum chamber, and the gas for generating plasma and enhancing the target gas are enhanced. It can also be introduced as required.
As the carrier gas, an inert gas composed of argon gas or helium gas can be contained.

  As a low-temperature plasma generator used in the present invention, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma is used. In order to obtain highly active and stable plasma, a high-frequency plasma generator is used. It is desirable to do.

The vapor deposition conditions in the plasma chemical vapor deposition method will be further described. The vacuum chamber is depressurized by a vacuum pump, and the degree of vacuum is 1 × 10 ⁻² to 1 × 10 ² Pa, preferably the degree of vacuum is 1 × 10 ^−1. It is preferable to adjust to ˜1 × 10 ¹ Pa, and the conveyance speed of the base film is related to the film thickness, density, productivity, etc. of the continuously deposited film of the organic silicon oxide to be formed, and is usually 10 to 10. It is preferable to adjust to 500 m / min, preferably 50 to 350 m / min. The plasma generation voltage is usually adjusted to 10 to 50 kW in relation to the film thickness, density, productivity, and the like of the organic silicon oxide continuous vapor deposition film layer to be formed.

[Gas barrier layer]
In the present invention, it is excellent in long-term storability even when using a cataplasm packaging outer package whose gas barrier property is about the same as the conventional one or inferior in gas barrier property, by making the cataline liner excellent in gas barrier property. For the purpose of providing a gas barrier property on the continuous vapor deposition film layer of the carbon-containing organosilicon oxide, which is a gas barrier layer having excellent adhesion to the base film, in order to obtain an innocuous patch preparation package. A gas barrier coating film is formed by applying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method with or without an organic silicon oxide vapor-deposited thin film. is there. Thereby, the gas barrier property can be further improved.

[Deposition layer of organosilicon oxide]
In the present invention, an organic silicon oxide vapor-deposited layer can be used to provide gas barrier properties. Specifically, an organic silicon compound that is an organic compound of silicon (Si) is used as the organic silicon oxide deposition layer. Moreover, an organic silicon compound can be used by 1 type, or 2 or more types of mixtures as a vapor deposition material to be used, and a vapor deposition layer can be comprised using the organosilicon compound mixed by the dissimilar material.

  In the present invention, as a method for providing an organic silicon oxide vapor deposition layer on the surface of a base film, for example, chemical vapor deposition methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition Can be mentioned.

An organic silicon oxide vapor-deposited layer is formed by depositing an organic silicon compound on a film on which a continuous vapor-deposited carbon-containing silicon oxide layer is formed by plasma CVD guided on a cooled coating drum. As a vapor deposition material, a continuous vapor deposition film of organosilicon oxide is laminated by a chemical vapor deposition method, a vapor deposition layer is multilayered on a base film, and the vapor deposition layer multilayer film is wound on a winding roll, or subsequently, a vapor deposition layer It is also possible to form a gas barrier coating film on the vapor deposition surface of the multilayered film by a sol-gel method, heat-dry it to obtain a final gas barrier multilayer film, and wind it on a winding roll. The illustration shows an example, and the present invention is not limited thereby.

  After forming an organic silicon oxide vapor-deposited layer by the chemical vapor deposition method on a film on which an organic silicon oxide gas barrier continuous vapor-deposited film is formed, the vapor-deposited layer is further subjected to glow discharge treatment, plasma treatment or microwave treatment. May be. Thereby, the adhesiveness of a vapor deposition layer and the following gas-barrier coating films further improves.

In the present invention, a dense gas barrier layer with improved tight adhesion can be obtained by laminating a primer layer on a continuously deposited organic silicon oxide film layer.
In particular, a vapor-deposited layer of organic silicon oxide is laminated by chemical vapor deposition, and a gas barrier composition obtained by polycondensation of the alkoxide of the present invention and a water-soluble polymer by sol-gel method is applied. When a gas barrier coating film is laminated, a gas barrier multilayer film having extremely excellent moisture and heat resistance and tight adhesion can be obtained.

  In the present invention, as the film thickness of the organic silicon oxide continuous vapor deposition film layer formed as the gas barrier layer, including the film thickness of the organic silicon oxide gas barrier layer formed by the plasma CVD method, for example, 5 to 100 nm, Preferably, it is desirable to select and form arbitrarily within the range of 10 to 50 nm. If the thickness is less than 5 nm, the formation of the continuous vapor deposition film layer may be insufficient, and the gas barrier property may not be sufficient. If the thickness exceeds 100 nm, cracks are likely to occur and flexibility is reduced.

[Gas barrier coating]
Next, the gas barrier coating film constituting the gas barrier layer of the present invention will be described.
The gas barrier coating film of the present invention contains an alkoxide and a water-soluble polymer. Specifically, the gas barrier coating film is represented by the general formula: R ¹ _n M (OR ² ) _m. A gas barrier composition obtained by polycondensation of a composition containing at least one alkoxide, polyvinyl alcohol and / or ethylene / vinyl alcohol by a sol-gel method is applied onto the above-mentioned vapor-deposited organic silicon oxide film. And dried by heating.

The alkoxide that can be suitably used in the present invention has a general formula: R ¹ nM (OR ² ) m (wherein M is a metal atom, R ¹ and R ² are organic groups having 1 to 8 carbon atoms, n is 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one of alkoxide partial hydrolyzate or alkoxide hydrolysis condensate can be used.

As the metal atom represented by M in the general formula: R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum and the like can be used, and preferably silicon. These alkoxides can be used singly or in combination of two or more different metal atoms in the same solution.

Specific examples of the organic group R ¹ include, for example, methyl group, ethyl group, n-propyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group. And alkyl groups such as a group, n-hexyl group, and n-octyl group. Specific examples of the organic group R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. In the present invention, these alkyl groups in the same molecule may be the same or different.
Among the alkoxides, an alkoxysilane in which M is Si is preferable, and the alkoxysilane is represented by Si (OR ^a ) ₄ , and R is a lower alkyl group. As R ^a , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like are used. Specific examples of alkoxysilane include 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 and the} like.

The alkyl alkoxysilane R ^b _m Si can be used _{^{(OR c) 4-m (}} m is an integer of 1, 2, 3). As R ^b and R ^c , a methyl group, an ethyl group or the like is used. Specific examples of the alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH ₃ ) ₂ dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) _{2 and the} like. These alkoxysilanes and alkylalkoxysilanes can be used alone or in combination of two or more.

Furthermore, polycondensation products of alkoxysilanes can be used, and specific examples include polytetramethoxysilane and polytetraemethoxysilane.
Two or more kinds of these alkoxides may be mixed and used. In particular, the use of a mixture of alkoxysilane and zirconium alkoxide improves the toughness, heat resistance, and the like of the resulting laminated film. In particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting coating film is lowered, and the heat resistance of the base film is remarkably improved.

  In order to prepare a gas barrier composition for forming a barrier coat according to the present invention, a silane coupling agent and the like can be added together with the alkoxide. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. Particularly preferred are organoalkoxysilanes having an epoxy group, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Can be suitably used. Two or more kinds of such silane coupling agents may be mixed and used. Moreover, the usage-amount of a silane coupling agent exists in the range of 0.1-20 weight part with respect to 100 weight part of said alkoxysilanes. When 20 parts by weight or more is used, the rigidity and brittleness of the formed composite polymer are increased, and the insulating properties and workability of the coating layer are lowered.

In the present invention, the water-soluble polymer is important because a dense film structure having excellent gas barrier properties can be obtained and a method for easily producing an excellent gas barrier coating film can be realized.
The water-soluble polymer used when producing the composition for forming a gas barrier coating film (coating liquid) includes polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance and the like of the resulting coating film are remarkably improved. Furthermore, a coating film obtained by combining polyvinyl alcohol and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties, water resistance, and weather resistance.

When the combination of polyvinyl alcohol and ethylene / vinyl alcohol copolymer is employed, the weight ratio of each is preferably 10: 0.05 to 10: 6, more preferably about 10: 1.
The total content of the polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight, preferably about 50 to 400 parts by weight, based on 100 parts by weight of the total amount of the alkoxide. If it exceeds 500 parts by weight, the brittleness of the composite polymer increases, and the water resistance and weather resistance of the resulting coating film also deteriorate. When the amount is less than 5 parts by weight, the gas barrier property is lowered.

  In this invention, the said composition (coating liquid) is apply | coated on a vapor deposition layer, The composition is polycondensed by the sol-gel method, and a coating film is obtained. As the sol-gel method catalyst, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is mainly used as a polycondensation catalyst. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and N, N-dimethylbenzylamine is particularly preferable. The amount used is 0.01 to 1 part by weight, preferably about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxide and silane coupling agent. Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid and tartaric acid. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, etc. can be used, for example.

  Furthermore, regarding the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. The kind of organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, one commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be used.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000), an RS polymer manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = manufactured by Kuraray Co., Ltd.). 2000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,000), and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Specific examples include 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.

[Method for forming gas barrier coating film]
Alkoxides such as alkoxysilanes, silane coupling agents, polyvinyl alcohol resins and / or ethylene / vinyl alcohol copolymers, hydrochloric acid, water, organic solvents, and, if necessary, metal alkoxides as sol-gel method catalysts A gas barrier composition coating solution is prepared by mixing. When this gas barrier composition is applied on a continuous vapor deposition film layer of organosilicon oxide and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the alkoxide, metal alkoxide, silane coupling agent and vinyl are removed. The polycondensation reaction of the alcohol polymer further proceeds and is completed, and a transparent gas barrier coating film is formed. Further, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the carbon-containing organosilicon oxide deposition layer, the organosilicon oxide continuous deposition film layer and the gas barrier property Adhesiveness with a coating film, adhesiveness, etc. will become favorable.

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

  In the present invention, the alkoxide hydrolyzate and the water-soluble polymer form a chemical bond, a hydrogen bond, a coordination bond, or the like by hydrolysis and cocondensation in the gas barrier coating film to cause a crosslinking reaction. In addition, it is considered that the water-soluble polymer is crystallized, and the vapor deposition layer and the gas barrier coating film are firmly adhered to each other by hydrogen bonding or chemical bonding. Adhesion between the two layers with the coating film is improved, and a better gas barrier effect can be exhibited by a synergistic effect.

  In the present invention, the gas barrier coating film-forming composition may be applied once or by a coating means such as a roll coat such as a gravure roll coater, spray coat, dipping, brush, bar coat, or applicator. A barrier coating having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed by a plurality of coatings. And the base film which provided the continuous vapor deposition film layer of the organosilicon oxide which apply | coated the said coating liquid is 20 to 250 degreeC, and the temperature below the melting | fusing point of a base film, Preferably it is 50 to 200 degreeC. In particular, heat treatment is performed at a temperature in the range of 150 ° C. to 200 ° C., more preferably 180 ° C. to 200 ° C. for 1 second to 10 minutes, preferably 1 second to 2 minutes, more preferably 30 seconds to 90 seconds. On the gas barrier continuous vapor deposition film of the organic silicon oxide formed on the material film, one or more gas barrier coating films are formed by the gas barrier composition (coating liquid) to form the gas barrier coating film. Constitute.

  Further, if necessary, when applying the gas barrier composition of the present invention, a primer agent or the like may be applied in advance on the organic silicon oxide continuous vapor deposition film layer.

Next, a cataplasm packaging outer package for packaging cataplasm using the cataplasma liner of the present invention as a peelable protective film will be described.
The patch packaging exterior body is a bag made of a multilayer laminated film for a packaging exterior body in which a gas barrier film having the same gas barrier laminate structure as the patch agent liner and a light shielding or light shielding film are laminated using an adhesive. Is.

  The gas barrier film can be produced in the same manner as already described for the poultice liner. The difference from the poultice liner is that an organic silicon oxide peelable continuous vapor deposition film layer is not formed.

  Below, the material and manufacturing method of a light-shielding or light-blocking laminated resin film, a laminating film for a poultice packaging outer package, and a cataplasm outer packaging are described.

[Light-shielding or light-shielding laminated resin film]
As the light-shielding or light-shielding laminated resin film (20) in the present invention, the first white resin layer (21) made of a resin composition containing at least a thermoplastic resin and a white colorant, at least the thermoplastic resin and black A black resin layer (22) made of a resin composition containing a colorant and a second white resin layer (21) made of a resin composition containing at least a thermoplastic resin and a white colorant were coextruded and laminated in this order. If it is a laminated resin film having a layer structure as a basic structure, a laminated structure in which other layers are further laminated may be used. For example, a thermoplastic resin layer obtained by further laminating a first thermoplastic resin layer made of a resin composition containing at least a thermoplastic resin as a main component of a vehicle, or a resin composition containing at least a thermoplastic resin as a main component of a vehicle. The laminated resin film which consists of the structure which carried out the coextrusion lamination | stacking on the both sides of the laminated resin film of the said basic structure can be illustrated. The above illustrations illustrate a few examples of the laminated resin film in the present invention, and the present invention is not limited to this.

  The laminated resin film in the present invention basically has strength and the like, and is excellent in various physical properties such as weather resistance, heat resistance, water resistance, heat sealability, and particularly, sealant property, light shielding. It is required to have excellent properties or light blocking properties. For example, it acts as a light-blocking or light-blocking layer that blocks sunlight or fluorescent light from being transmitted by the sun or fluorescent lamps, etc., and prevents the contents from being decomposed or altered, or causing light degradation such as fading. In addition, it acts as a heat sealant layer at the time of bag making and the like, and has contents filling and packaging suitability, storage suitability and the like. Furthermore, it does not generate harmful substances when incinerated and discarded after use, and is extremely excellent in disposal and environmental suitability.

  The laminated resin film in the present invention will be described more specifically. In the laminated resin film of the present invention, the first and second white resin layers are basically mainly a concealing layer that conceals the black resin layer, and It acts as a light-blocking or light-blocking layer that reflects or diffuses sunlight or fluorescent light from the sun or a fluorescent lamp and blocks its transmission. Further, the first white resin layer acts as a base layer for making a printed pattern clear when, for example, a printed pattern such as a desired character, symbol, pattern, or figure is directly or indirectly formed thereon. The second white resin layer acts as a heat sealable resin layer or the like that forms a seal portion or the like when making bags. Next, the black resin layer basically acts synergistically with the white resin layer, and absorbs sunlight or fluorescence from the sun or a fluorescent lamp and blocks light from passing therethrough. It acts as a light blocking layer or the like.

  Further, the first and second thermoplastic resin layers of the modification mainly function as a protective layer for protecting the first and second white resin layers or the black resin layer, or a concealing layer for concealing them. Furthermore, the thermoplastic resin layer is formed as a base layer for making the printed pattern clear or when making a printed pattern such as a desired character, symbol, pattern, figure or the like directly or indirectly on the thermoplastic resin layer. At this time, it acts as a heat-sealable resin layer or the like.

  In the present invention, since the laminated resin film is aluminum-free, it does not generate harmful substances when incinerated and discarded after use, and is extremely excellent in disposal and environmental suitability. Further, it has an advantage of facilitating the inspection of metal pieces (foreign matter) using a metal detector or the like. In the present invention, although not shown, it is possible to design and manufacture laminated resin films having various forms by arbitrarily laminating other base materials depending on the purpose of use, application, etc. It is.

  Next, the material, the manufacturing method, etc. which comprise the laminated resin film in this invention are demonstrated. First, as the thermoplastic resin forming the first and second white resin layers, the black resin layer, and the first and second thermoplastic resin layers constituting the laminated resin film in the present invention, for example, by heat It is possible to use a mixture of one or more thermoplastic resins that can be melted and extruded from an extrusion die such as an extruder and can be heat-sealed to each other.

  Specifically, for example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using a multisite catalyst, LLDPE), polymerization using a metallocene catalyst (single site catalyst) Ethylene-α / olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-acrylic acid Polyolefin resins such as ethyl copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene are treated with acrylic acid, methacrylic acid. , Maleic acid, Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as hydromaleic acid, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, thermoplastic polyester resin, heat One or more thermoplastic resins such as a plastic polyamide resin can be used.

  The 1st, 2nd white resin layer, the 1st, 2nd thermoplastic resin layer which comprises the laminated resin film in this invention using 1 type, or 2 or more types of the said thermoplastic resin in this invention Each layer has an affinity between each layer, and during coextrusion molding, each layer is firmly and tightly bonded, and has excellent strength, and various properties such as weather resistance, heat resistance, water resistance, etc. A laminated resin film having excellent physical properties can be constituted. Further, one of the first and second white resin layers or the first and second thermoplastic resin layers is composed of a thermoplastic resin that can be thermally fused to each other. It acts as a heat-sealable resin layer for forming a seal portion or the like when the outer package is made, and can form a very good seal portion or the like.

  As the white and black colorants of the colored resin layer constituting the laminated resin film in the present invention, the white colorant, for example, reflects or diffuses sunlight or fluorescent light of a fluorescent lamp and prevents its transmission. In addition, it is intended to prevent the degradation or alteration of the contents packed and packed in the package, or the light deterioration such as fading, and specifically, for example, various white type inorganic or organic dyes A mixture of one or more colorants such as pigments can be used. In the present invention, for example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatase titanium oxide, rutile titanium oxide, calcium carbonate, zinc oxide, One or more of white pigments such as barium sulfate can be used. The amount of use is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the thermoplastic resin in the resin composition constituting the first and second white resin layers. % Can be used.

  Next, for the black colorant, for example, it absorbs sunlight or fluorescent light from fluorescent lamps (mainly absorbs the visible region from near ultraviolet), blocks or blocks its transmission, and is packed and packed in a packaging bag. It is intended to prevent degradation or alteration of contents, or light deterioration such as discoloration. Specifically, for example, one kind or a mixture of two or more kinds of colorants such as various black type inorganic or organic dyes and pigments can be used. In the present invention, for example, one or more kinds of black pigments such as iron black, graphite, carbon black, and electrically conductive materials (polyaniline, polypyrrole) can be used. The amount used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight added to the thermoplastic resin in the resin composition constituting the black resin layer. be able to.

  In addition, as a black resin layer which comprises a laminated resin film etc. in this invention, the gray resin layer which uses the mixture of the said black type colorant and the said white type colorant can also be used, for example. That is, as the gray resin layer constituting the laminated resin film in the present invention, a gray resin layer comprising a resin composition containing at least a thermoplastic resin, a black colorant, and a white colorant is used. The black pigment can be used in an amount of 0.1 to 10.0% by weight and the white pigment can be added in an amount of 0.1 to 30.0% by weight with respect to the thermoplastic resin in the resin composition.

  The resin composition containing the thermoplastic resin constituting the laminated resin film and the colorant in the present invention will be described. For example, one or more of the thermoplastic resins as the main component of the vehicle is one of the colorants. When necessary, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, and slipperiness in the resin composition to which seeds or two or more are added. In order to improve and improve the peelability, flame retardancy, antifungal property, electrical properties, strength, etc., one or more kinds of various plastic compounding agents and additives are optionally added, If necessary, a solvent, a diluent and the like can be added.

  Examples of the plastic compounding agent and additive include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a flame retardant, a flameproofing agent, a foaming agent, Molding agents, pigments, dyes, dispersants, surfactants, antiblocking agents and the like can be used, and further, modifying resins and the like can be used. The addition amount can be arbitrarily added from a very small amount to several tens of weight% according to the purpose.

Next, a method for producing the laminated resin film in the present invention will be described.
First, a resin composition containing a thermoplastic resin corresponding to each thermoplastic resin layer constituting the laminated resin film and a colorant is prepared, and then each resin composition is mixed with, for example, a T-die coextrusion machine or an inflation copier. A laminated resin film is produced by coextrusion using an extruder or the like. For example, the first layer is a first white resin layer made of a resin composition containing at least a thermoplastic resin and a white colorant, and the second layer is black made of a resin composition containing at least a thermoplastic resin and a black colorant. In the present invention, the resin layer and the third layer are composed of two types and three layers, each of which has a structure in which three layers are coextruded and laminated in order of a second white resin layer made of a resin composition containing at least a thermoplastic resin and a white colorant. A laminated resin film can be manufactured.

  The above illustration shows an example of the method for producing a multilayer laminated resin film in the present invention, and the present invention is not limited to this. Moreover, when producing the laminated resin film in the present invention, further, depending on the purpose of use, application, etc., other materials are used, and this is arbitrarily co-extruded to design laminated resin films having various forms. Can be manufactured.

  The thickness of the laminated resin film in the present invention is about 9 μm to 120 μm, preferably 10 μm to 60 μm. In the laminated resin film, the thickness of each layer constituting the first resin layer is such that the first and second white resin layers are in the range of 3 to 40 μm, preferably 4 to 30 μm. When the film thickness is less than 3 μm, it becomes difficult to conceal the black resin layer, and the appearance and aesthetics are deteriorated. When a printed pattern layer is provided on the white resin layer, the printed pattern layer, etc. This is not preferable because the gradation or color tone is affected, and the function as the heat-sealable resin layer is also lowered. On the other hand, when the film thickness exceeds 40 μm, the concealment property of the black resin layer is improved, but the overall thickness is increased, and the influence on the environment as packaging dust or the like may be increased.

  The black resin layer has a thickness in the range of 2 μm to 40 μm, preferably 3 μm to 30 μm. If the film thickness is less than 2 μm, the function as a light-shielding or light-shielding layer or the like is deteriorated, and further, there is a possibility of causing a problem that it is greatly affected by thickness unevenness, and thus it is not preferable. On the other hand, when the film thickness exceeds 40 μm, the light shielding property or the light shielding property is improved, but it is not preferable because it becomes difficult to set and select a concealing resin layer or a white resin layer for concealing it. .

  The first and second thermoplastic resin layers have a film thickness of 3 μm to 40 μm, preferably 4 μm to 30 μm. When the film thickness is less than 3 μm, it is difficult to perform functions such as protection and concealment, and the appearance and aesthetics are deteriorated, and the function as a heat-sealable resin layer is also decreased. For reasons such as this is not preferable. On the other hand, if the film thickness exceeds 40 μm, the entire layer thickness becomes large, which is not preferable for disposal when discarded.

  In the present invention, sunlight or the like is absorbed by one of the light-blocking or light-blocking layers composed of two layers of the white resin layer and the black resin layer or two layers of the white resin layer and the gray resin layer. At the same time, the other layer reflects or diffuses sunlight, etc., and the synergistic effect of the two layers completely blocks or blocks the transmission of sunlight or fluorescent light, etc. Therefore, it is possible to further prevent light degradation such as decomposition or alteration of the contents or fading.

  Furthermore, in the present invention, one of the white resin layers has a function such as a base layer of a printed pattern layer provided directly or indirectly thereon, and a character, figure, Heat-sealability that makes printed images such as symbols and designs clearer and reproduces or reveals beautiful printed patterns, and the other side of the white resin layer forms a sealing part during bag making etc. It can also function as a resin layer.

  Further, in the present invention, the thermoplastic resin layer constitutes a transparent or translucent or opaque layer, and protects or hides the white resin layer or the black resin layer, and one of the thermoplastic resin layers is It will also have the functions of the underlying layer of the printed pattern layer provided directly or indirectly on it, making the printed images such as letters, figures, symbols, and patterns that make up the printed pattern layer even clearer and beautiful The printed pattern can be reproduced or manifested, and the other of the thermoplastic resin layers can also function as a heat-sealable resin layer that forms a seal portion or the like during bag making.

  As is clear from the above description, the laminated resin film in the present invention has strength and the like, and is excellent in various physical properties such as weather resistance, heat resistance and water resistance, and in particular, excellent in light shielding properties or light blocking properties. In addition, it has excellent heat sealability, suitability for packaging and storage of contents, storage suitability, etc. Furthermore, it is suitable for disposal, environmental suitability, etc. without generating harmful substances when incineration disposal after use In addition, the laminated resin film in the present invention does not react with a metal (foreign matter) detector, etc., and facilitates inspection of metal pieces (foreign matter), and is suitable for the production of a packaging exterior body. It is.

[Multilayer laminated film for cataplasm packaging outer packaging]
The light-shielding or light-blocking laminated resin film in the present invention and the gas barrier film described in the patch agent liner in the present invention are laminated to produce a multilayer laminate film for a cataplasm packaging outer body. In the case of using the light-shielding or light-shielding film for the film, first, a light-shielding or light-shielding film is provided on the gas barrier coating layer of the gas barrier film, for example, via an adhesive layer for lamination. The multilayer laminated film for the cataplasm packaging outer package in the present invention can be manufactured.

  Moreover, in this invention, you may form the printing pattern layer which consists of a desired character, a symbol, a design, a figure, etc. in the back surface which consists of corona treatment etc. of a gas barrier film. The printed pattern layer may be formed before or after the gas barrier laminate film is formed, or before or after the light shielding or light blocking laminate resin film is laminated. The above illustration shows an example of the multilayer laminated film for a cataplasm packaging outer body in the present invention, and the present invention is not limited to this. For example, a printed pattern layer composed of desired characters, symbols, patterns, figures, etc. is formed on the surface of the white resin layer or the thermoplastic resin layer constituting the light-blocking or light-blocking laminated resin film in the present invention. Thereafter, a gas barrier film can be laminated on the surface including the printed pattern layer via a laminating adhesive layer or the like to produce a multilayer laminated film for a cataplasm packaging outer body in the present invention.

  Examples of the method for producing a multilayer laminated film for a cataplasm packaging outer body in the present invention include, for example, a dry laminate lamination method in which layers are arbitrarily laminated through a primer layer or an adhesive layer for lamination, or a primer layer or an anchor coat layer. By using a laminating method such as an extrusion laminating method in which various resins are melt-extruded and laminated arbitrarily, a multi-layer laminated film for a poultice packaging exterior body can be produced.

  The laminating adhesive layer according to the present invention will be described. Examples of the laminating adhesive include polyvinyl acetate adhesive, homopolymers such as ethyl acrylate, butyl, 2-ethylhexyl ester, and methacrylic acid. Copolymerization of polyacrylic acid ester adhesive, cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, and other monomers consisting of copolymers with methyl acid, acrylonitrile, styrene, etc. Ethylene copolymer adhesives made of coalescence, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenolic resin adhesives Epoxy adhesive, polyurethane adhesive, anti Type (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, etc., silicone adhesive, alkali metal silicate, inorganic adhesive made of low melting point glass, etc. Can be used. The composition system of the adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type.

In addition, the properties may be any form such as film / sheet, powder, solid, etc., and the adhesion mechanism is any form such as chemical reaction type, solvent volatilization type, heat melting type, hot pressure type, etc. But that's fine. The adhesive can be applied, for example, by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or a printing method, and the coating amount is 0.1 to 10 g / m ² (dry state). The position is desirable.

The anchor coat layer according to the present invention will be described. As the anchor coat agent, for example, various aqueous or oil-based anchor coat agents such as organic titanates such as alkyl titanates, isocyanates, polyethyleneimines, and polyptadiene are used. be able to. As the anchor coating agent, for example, a coating method such as roll coating, gravure roll coating, kiss coating or the like can be used, and the coating amount is preferably about 0.1 to 5 g / m ² (dry state).

  Examples of the melt-extruded resin layer in the extrusion laminate lamination method include, for example, a polyethylene resin, a polypropylene resin, an acid-modified polyethylene resin, an acid-modified polypropylene resin, an ethylene-acrylic acid or methacrylic acid copolymer, and a Surlyn type. One or more thermoplastic resins such as resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin Can be used. In the extrusion lamination lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coat layer such as the anchor coat agent.

  In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminated material. The printed pattern layer is mainly composed of one or more ordinary ink vehicles, and, if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, and a curing agent. Add one or more additives such as crosslinking agents, lubricants, antistatic agents, fillers, etc., and add colorants such as dyes and pigments, and use solvents, diluents, etc. Kneading to prepare an ink composition, and then using the ink composition, for example, using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. A desired printed pattern composed of characters, figures, symbols, patterns, etc. can be printed on the thin film to form the printed pattern layer in the present invention.

  In the present invention, as the primer layer, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin such as polyethylene or polypropylene The primer layer can be formed by using a resin composition having a main component of the vehicle, such as a resin based on resin or a copolymer or modified resin thereof, or a cellulose resin.

In the present invention, for example, the primer coat layer can be formed using a coating method such as roll coating, gravure roll coating, kiss coating, etc., and the coating amount is 0.1 to 10 g / m ² (dry state). ) Is desirable. Moreover, in this invention, when performing lamination | stacking, if necessary, pre-treatments, such as a corona treatment and an ozone treatment, can be given to a film.

[Patch preparation package]
Next, an example of the poultice packaging body of the present invention produced by making a bag using the multilayer laminated film for a cataplasm packaging outer body in the present invention will be described.
As illustrated in the present invention, as a package, a package produced using a multilayer laminated film for a packaging exterior body is manufactured by the multilayer lamination for a packaging exterior body according to a conventionally used bag making method. Two films are prepared, the surfaces of the second white resin layer located in the innermost layer are opposed to each other, and then the second white resin layer is allowed to act as a heat-sealable resin layer. A three-side-sealed bag-shaped packaging exterior body is manufactured by heat-sealing the three sides of the peripheral edge and providing an opening above the three sides.

  In the present invention, from the opening of the produced three-side-seal type bag-shaped package exterior body, the poultice using the poultice liner in the present invention as a protective film is filled, and then the end of the upper opening is heat-sealed. Then, the cataplasm packaging body which consists of various forms in this invention is manufactured.

  In addition, it cannot be overemphasized that the package in this invention is not limited to the shape of the package shown in figure, A two-side seal type | mold, a four-side seal type | mold, self-supporting property according to the objective, a use, etc. Needless to say, it is possible to manufacture packages having various forms such as a mold, a gusset mold, and a square bottom mold.

Hereinafter, the present invention will be described in more detail by way of examples.
[Measuring method]
The water vapor permeability, the adhesive sensory evaluation and the cooling effect sensory evaluation of the poultice liner film prepared in the examples were tested and evaluated by the following measurement methods or evaluation methods.

[Measurement of water vapor permeability]
Carbon-containing organosilicon on a gas barrier film provided with a gas barrier layer such as a gas barrier continuous vapor deposition film layer and a gas barrier coating layer of a carbon-containing organosilicon oxide on one side of a plastic substrate film such as a polyester film by plasma CVD The water vapor permeability of the liner provided with the oxide peelable continuous vapor deposition film layer was measured.

The water vapor transmission rate was measured using a water vapor transmission rate measurement device (manufactured by MOCON, USA, PERMATRAN 3/31) under the conditions of a measurement temperature of 40 ° C. and a humidity of 90% RH in accordance with JIS K7129. In addition, the detection limit of the water vapor transmission rate measuring apparatus used for the measurement is 0.02 g / m ² · day.

[Sensory evaluation of adhesive strength]
The unsealed sample containing the cataplasm was stored for 3 months in an environment of 25 ° C. and 60% RH, and then sensory evaluation of the adhesive strength to the skin (comparison with the initial adhesive strength) was performed.

[Sensory evaluation of cooling effect]
The opened sample containing the cataplasm was stored for 3 months in an environment of 25 ° C. and 60% RH, and then the sensory evaluation of the cooling effect on the skin (comparison with the initial cool feeling) was performed.

[Thickness of laminated film]
The cross section of the laminated polyester film was cut into ultrathin sections, observed with a TEM (transmission electron microscope), photographed, and the thickness was measured with the photographed cross section.

[Example of formation of gas barrier continuous vapor deposition film layer of carbon-containing organosilicon oxide]
In the present invention, a high-frequency plasma chemical vapor deposition method (high-frequency plasma CVD method) is used to form a gas barrier continuous vapor deposition film layer of carbon-containing organosilicon oxide. When a continuous vapor deposition film layer of carbon-containing organosilicon oxide is formed by a high-frequency plasma CVD method, first, the base film is mounted on a feed roll of a roll-up type plasma chemical vapor deposition apparatus, and the gas barrier property of the film The surface on which the vapor deposition layer is formed is subjected to corona discharge treatment, or the corona treatment surface of the corona-treated substrate film is 10 nm thick using a high-frequency plasma chemical vapor deposition method under the conditions shown below. A continuous vapor deposition film layer of carbon-containing organosilicon oxide was formed.
Deposition conditions:
Deposition surface: Corona-treated surface Introduction gas mixing ratio; Hexamethyldisiloxane: Oxygen gas: Helium: Argon = 1.2: 0.5: 5.0: 0.5 (unit: slm)
Deposition pressure: 2.3 × 10 ⁰ Pa
Deposition rate: 200 m / min
Power: 15kW

[Formation example of gas barrier coating layer]
For the formation of the gas barrier coating film of the gas barrier layer, according to the composition shown below, ethyl silicate (ethyl ethyl silicate), ethyl alcohol, 2N normal hydrochloric acid aqueous solution and ion-exchanged water are mixed and stirred at room temperature for about 1 hour. Prepare composition a, and then add epoxy silane coupling agent SH6040, ethylene-vinyl alcohol (Soarnol 30L) (manufactured by Nippon Gosei Kagaku), N, N-dimethylbenzylamine, and stir for 30 minutes. A colorless and transparent gas barrier coating film-forming composition coating liquid was obtained.
The formation of the gas barrier coating film is performed by coating the aluminum oxide vapor-deposited layer or the plasma-treated surface with the coating liquid of the prepared gas barrier coating film-forming composition by the gravure roll coating method, and then 150 ° C. for 1 minute. A gas barrier coating film having a thickness of 0.3 μm (dry state) was formed by heat drying.
Barrier coating solution composition:
Composition a Ethyl silicate (normal ethyl silicate) 34.13
Ethyl alcohol 25.00
2N aqueous hydrochloric acid solution 1.15
H ₂ O 4.58
Silane coupling agent (SH6040 manufactured by Toray Dow Corning) 3.41
Composition b Polyvinyl alcohol (Soarnol 30 L) 31.56
N, N-dimethylbenzylamine 0.17
Total (wt%) 100.00

[Formation example of peelable continuous vapor deposition film layer]
When forming a continuous vapor-deposited film of carbon-containing organosilicon oxide by the high-frequency plasma chemical vapor deposition method (high-frequency plasma CVD method) of the embodiment of the present invention, first, the substrate film is wound up by plasma chemical vapor deposition A high-frequency plasma CVD method that is mounted on a feeding roll of a growth apparatus and is subjected to corona discharge treatment on the surface on which the deposited layer of the film is formed or on the corona treatment surface of the corona-treated film under the conditions shown below. Was used to form a continuous vapor deposition film layer of carbon-containing organosilicon oxide having a thickness of 10 nm.
Deposition conditions:
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium: Argon = 10: 1: 10: 10 (unit: slm)
Deposition pressure: 1.8 × 10 ⁰ Pa
Deposition rate: 200 m / min
Power: 15kW

Example 1
[Manufacture of poultice liners]
A biaxially stretched polyethylene terephthalate film with a thickness of 38 μm, which is easy-adhesive on one side, is mounted on a feed roll of a roll-up type plasma CVD vapor deposition apparatus, and the above [gas barrier property of carbon-containing organosilicon oxide] Gas barrier continuous vapor deposition of carbon-containing organosilicon oxide having a thickness of 10 nm using hexamethyldisiloxane (HMDSO) as a vapor deposition monomer material by high-frequency plasma CVD under the vapor deposition conditions described in Example of formation of continuous vapor deposition film layer] A film layer was formed to obtain a gas barrier film.

  Next, on the gas barrier layer of the gas barrier film, a carbon-containing organosilicon oxide having a releasability of 8 nm in thickness by a high-frequency plasma CVD method under the vapor deposition conditions described in [Example of formation of peelable continuous vapor deposition layer]. Thus, a catalyzer liner of the present invention was produced.

Here, in order to evaluate the water vapor permeability as a gas barrier property of the produced cataplasm liner, the water vapor permeability was measured according to the method for measuring the water vapor permeability. As a result of the measurement, the water vapor permeability was 1.7 g / m ² · day, and a poultice liner having excellent gas barrier properties was obtained.

[Preparation of gas barrier film for cataplasm packaging packaging]
Hexamethyldisiloxane (HMDSO) was formed on one side of a 12 μm-thick biaxially stretched polyethylene terephthalate film by high-frequency plasma CVD under the deposition conditions described in [Example of formation of gas barrier continuous vapor deposition layer of carbon-containing organosilicon oxide]. ) As a vapor deposition monomer material, a continuous vapor deposition film of carbon-containing organic silicon oxide having a thickness of 10 nm was formed, and the gas barrier organic silicon oxide continuous vapor deposition film layer was obtained. Next, a gas barrier coat forming composition similar to that used in [Example of formation of gas barrier coating film] on the continuous vapor deposition film layer of the gas barrier organic silicon oxide was formed to a thickness of 0.3 μm by the above method. A gas barrier coating film comprising a composite polymer layer was formed to produce a gas barrier film.

[Production of light-shielding or light-shielding laminated resin film]
(1) First, the following resin compositions (a) to (c) were prepared.

(A) Ethylene-α-olefin copolymer polymerized using a single site catalyst (metallocene catalyst) [Mitsui Chemicals, trade name, Evolue SP2020, density, 0.916 g / m ³ , melt flow rate (MFR) 1.5 g / 10 min] 85.0 parts by weight, titanium oxide 15.0 parts by weight as a white pigment, synthetic silica 0.5 parts by weight, erucic acid amide 0.05 parts by weight, ethylene A resin composition constituting the first layer was prepared by sufficiently kneading 0.05 part by weight of bisoleylamide.

(B) Ethylene-α-olefin copolymer polymerized using a single site catalyst (metallocene catalyst) [Mitsui Chemicals, trade name, Evolue SP2020, density, 0.916 g / m ³ , melt flow rate (MFR) 1.5 g / 10 min] 98.5 parts by weight, 1.5 parts by weight of carbon black as a black pigment, and 0.05 parts by weight of erucamide are sufficiently kneaded, and the second layer is formed. A constituent resin composition was prepared.

(C) Ethylene-α-olefin copolymer polymerized using a single site catalyst (metallocene catalyst) [Mitsui Chemicals, trade name, Evolu SP2020, density, 0.916 g / m ³ , melt flow rate (MFR) 1.5 g / 10 min] 85.0 parts by weight, titanium oxide 15.0 parts by weight as a white pigment, synthetic silica 0.5 parts by weight, erucic acid amide 0.05 parts by weight, ethylene A resin composition constituting the third layer was prepared by sufficiently kneading 0.05 part by weight of bisoleylamide.

(2) Next, using the inflation co-extruder, the resin composition prepared in (a) to (c) was formed into a layer made of the resin composition of (a) to 20 μm, and the resin composition of (b). An unstretched multilayer laminated resin film consisting of three layers was produced by coextruding the layer to 10 μm and the layer of the resin composition (c) to 20 μm. The manufactured multilayer laminated resin film is milky white when viewed from the outside, is excellent in aesthetics, has sufficient light blocking properties or light blocking properties, hardly transmits each wavelength resulting from oxidation of fats and oils, and is extremely good. there were.

[Manufacture of multilayer laminated film for cataplasma exterior body and cataplasma exterior body]
The produced gas barrier laminate film and the produced light-shielding or light-shielding laminate resin film were coated with a urethane adhesive on the gas barrier layer and laminated to produce a multilayer laminate film for a cataplasm exterior body. Next, two sheets of the produced multilayer laminated film are overlapped to face each other, and the outer peripheral edge portion is three-way heat-sealed to form a seal portion, and a three-side seal type cataplasm packaging packaging body having an opening at the top. Manufactured.

  Next, in order to evaluate the peelability, adhesiveness and gas barrier properties and long-term storage stability required for a cataplasma liner and cataplasma package, a commercially available cataplasm is purchased and the liner affixed to the cataplasm is peeled off. The pap agent liner of the present invention in which a release layer is further formed on the gas barrier layer is used to make a pap agent, and the pap agent is stored in the prepared pap agent packaging exterior body, and the opening of the packaging exterior body is opened twice. Bent and fixed with tape.

After the sample of the unwrapped package of the cataplasm containing the cataplasm was stored for 3 months in an environment of 25 ° C. and 60% RH, the sensory evaluation of the adhesive strength to the skin (comparison with the initial adhesive strength) and the skin A sensory evaluation of the cooling effect on water (comparison with the initial cool feeling) was carried out and evaluated.
A summary of the above results is listed in Table 1. The sensory evaluation of the adhesive strength and cooling effect on the skin did not decrease even after 3 months, and had excellent adhesiveness, gas barrier properties and long-term performance. Preservability was shown.

Example 2
A biaxially stretched polyethylene terephthalate film with a thickness of 38 μm, which is easy-adhesive on one side, is mounted on a feed roll of a roll-up type plasma CVD vapor deposition apparatus, and the above [gas barrier property of carbon-containing organosilicon oxide] Gas-barrier continuous vapor deposition of carbon-containing organosilicon oxide having a thickness of 10 nm using hexamethyldisiloxane (HMDSO) as a vapor deposition monomer material by the high-frequency plasma CVD method under the vapor deposition conditions described in Example of Formation of Continuous Vapor Deposition Film Layer] A film was formed.

  Next, a gas barrier coating film was formed on the surface side subjected to the easy adhesion treatment. Regarding the formation of the gas barrier coating film, the polyvinyl alcohol aqueous solution of the composition b was added to the hydrolyzed solution of the composition a with stirring at the composition ratio described in [Example of formation of the gas barrier coating film layer], and the colorless transparent A coating liquid for the gas barrier coating film forming composition is obtained, and the coating liquid for the gas barrier coating film forming composition is applied to the continuous vapor deposition film layer (CVD method) of the carbon-containing organic silicon oxide. Coating was performed by a coating method, followed by heat-drying treatment at 150 ° C. for 1 minute to form a coating film having a coating thickness of 0.3 μm (dry state) to obtain a gas barrier coating layer. A gas barrier film having a gas barrier layer capable of achieving the gas barrier property required for the cataplasm liner of the present invention was obtained by forming a vapor barrier layer of an organic silicon compound and a series of gas barrier layers of a gas barrier coating film.

  Next, on the gas barrier layer of the gas barrier film, a peelability of 8 nm in thickness is formed by a high-frequency plasma CVD method under the vapor deposition conditions described in [Example of forming a peelable continuous vapor deposition layer] in the same manner as in Example 1. A peelable continuous vapor-deposited film of carbon-containing organosilicon oxide was formed to produce the catalyzer liner of the present invention.

In order to evaluate the water vapor permeability as a gas barrier property of the manufactured cataplasm liner, the water vapor permeability was measured according to the method for measuring the water vapor permeability. As a result of the measurement, the water vapor permeability was 0.6 g / m ² · day, the water vapor permeability was superior to that of Example 1, and a catalyzer liner having excellent gas barrier properties was obtained.

  Further, a multilayer laminated film for a cataplasm packaging outer packaging was produced in the same manner as in Example 1 to produce a cataplasm packaging outer packaging, while it was produced in Example 2 instead of the cataplasma liner produced in Example 1. Various sensory tests similar to Example 1 were performed and evaluated using the patch agent liner as a protective film for the patch.

  Table 1 summarizes the above results, and the sensory evaluation of the adhesive strength and cooling effect on the skin did not decrease even after 3 months, and showed excellent adhesiveness, gas barrier properties and long-term storage stability.

Comparative Example 1
A peelable layer was formed on the easy-adhesion surface side of a 50 μm polyethylene film that had been subjected to an easy-adhesion treatment on one side to obtain a protective film, which was replaced with a commercially available cataplasm.
Moreover, the cataplasm outer packaging body produced the laminated | multilayer film for exteriors which laminated | stacked the 7-micrometer-thick aluminum foil and the low-density polyethylene resin layer as a heat seal layer on the 50-micrometer-thick polyester base film (PET). Next, two sheets of the produced multilayer laminated film are overlapped to face each other, and the outer peripheral edge portion is three-way heat-sealed to form a seal portion, and a three-side seal type cataplasm packaging packaging body having an opening at the top. Manufactured.

  A sample of an unwrapped patch preparation containing a patch prepared by replacing the protective film with the polyethylene film in the prepared patch package outer package was stored for 3 months in an environment of 25 ° C. and 60% RH. The sensory evaluation of the adhesive strength to the skin (comparison with the initial adhesive strength) and the sensory evaluation of the cooling effect on the skin (comparison with the initial cool feeling) were carried out and evaluated. The results are shown in the table.

[Test results]
Using the resulting pack preparation package used in combination with the obtained patch preparation liner and coat preparation, the water vapor permeability was measured, and the sensory evaluation of the adhesive strength and cooling effect on the skin was carried out. The results are summarized in Table 1.

  The poultice liners obtained in Examples 1 and 2 showed excellent gas barrier properties, and both the sensory test of the adhesive strength of the cataplasm on the skin and the cooling effect when the cataplasm was applied to the skin were 3 months ago. There was no difference from the sticking feeling, and no decrease was observed. On the other hand, in the type which suppresses the functional deterioration of the cataplasm by the conventional exterior body, both the adhesive force and the sensory test of the cooling effect were clearly recognized to be reduced.

  From this, it was found that the long-term storability of the cataplasm can be sufficiently maintained or improved even when an aluminum foil having a gas barrier property lower than that used as the gas barrier layer is used as the cataplasm packaging exterior body.

  According to the gas barrier peelable film of the present invention, a strong chemical bond is formed between the base film and the deposited film, and a flexible organosilicon oxide deposited film having excellent adhesion is formed. The migration of medicinal components and moisture is suppressed, the flexibility of the vapor deposition film and the flexibility of the gas barrier coating film maintain the flexibility of the multilayer film and suppress the occurrence of cracks, and the gas barrier layer of the organosilicon oxide thin film Since the water repellency and moisture proofness have been improved by the synergistic action of the formation of the gas barrier multilayer film, the gas barrier property and the migration of the medicinal components are realized, and the protective function of the poultice is maintained.

  On the other hand, for Comparative Example 1, it is inferred that the cataplasm after opening has evaporated moisture from the appearance, and there is little fragrance of the drug, and the volatilization of the drug can be seen from the appearance, and when peeling the protective film, Peeling was lightened by drying the surface portion of the adhesive layer, and the adhesiveness with the skin was lowered, and the cooling effect when applied to the skin was also clearly reduced. In this way, storage using a combination of a conventional liner that does not impart gas barrier properties and an excellent gas barrier packaging with conventional aluminum foil does not prevent the evaporation of moisture and chemicals from the poultice, and long-term storage is sufficient. It wasn't.

  A gas-containing film having a gas-barrier layer on which a gas-barrier coating film layer of a carbon-containing organosilicon oxide is provided on a plastic base film of the present invention, and a gas-barrier coating layer is laminated thereon or not, is contained in a carbon-containing film. The liner on which a peelable continuous vapor-deposited film of organosilicon oxide is formed is not limited to a poultice liner, and can also be used in the general field of peelable protective films, as a conventional peelable peelable protective film. On the other hand, the cataplasm outer package is formed of a multilayer laminated film obtained by laminating a light-shielding or light-shielding film on the gas barrier film, and uses a combination of the cataplasma liner of the present invention and the packaging armor of the present invention. The body is excellent in gas barrier properties and long-term storage properties of poultices, and can replace conventional poultice packaging.

A: Patch agent liner A ′: Gas barrier film B: Multilayer laminated film C for packaging exterior body C: Packaging exterior body 1: Plastic substrate film 2: Gas barrier property continuous vapor deposition film layer 3: Peelable continuous vapor deposition film layer 4: Gas barrier coating layer 20: light shielding or light shielding laminated resin film 21: first or second white resin layer 22: black resin layer 30: seal portion

Claims (8)

  A gas barrier layer including at least a gas barrier continuous vapor deposition layer of an organic silicon oxide containing an organic component formed from a gas composition for vapor deposition containing an organosilicon compound on a plastic substrate film by a plasma vapor chemical vapor deposition method The gas barrier film has a peelable continuous vapor deposition film layer of an organosilicon oxide containing an organic component formed by a plasma chemical vapor deposition method from a gas composition for vapor deposition containing an organosilicon compound on the gas barrier layer. Patch agent liner.   The catalyzer liner according to claim 1, wherein the gas barrier layer further includes an organosilicon oxide vapor deposition layer and / or a gas barrier coating layer formed by chemical vapor deposition.   The poultice liner according to claim 2, wherein the gas barrier coating layer comprises a moisture and heat resistant gas barrier resin composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.   The organosilicon compound is 1,1,3,3-tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS), or hexamethyldisiloxane (HMDSO). Patch agent liner.   The liner for a poultice according to any one of claims 1 to 4, wherein the substrate is a biaxially stretched polyester film. A poultice packaging body using the poultice liner according to any one of claims 1 to 5 as a peelable protective film on the surface of the adhesive layer of the poultice and a packaging outer package for packaging the poultice. There,
The packaging outer package includes a gas barrier continuous vapor deposition film layer of an organic silicon oxide containing an organic component formed from a gas composition for vapor deposition containing an organic silicon compound on a plastic substrate film by a plasma vapor chemical vapor deposition method. Formed by sealing a multilayer laminated film for a packaging outer package including a gas barrier film formed by forming at least a gas barrier layer and a sealant light-shielding or light-blocking laminated resin film laminated on the gas barrier layer. A pack agent package comprising the pack agent using the patch agent liner and the pack agent package outer package, the pack agent being housed and packaged in the package outer package.   The cataplasm packaging material according to claim 6, wherein the gas barrier layer further includes an organic silicon oxide vapor deposition layer and / or a gas barrier coating layer formed by chemical vapor deposition.   The cataplasm packaging film according to claim 7, wherein the gas barrier coating layer comprises a moisture and heat resistant gas barrier resin composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.

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