JP2009262935A - Press through package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PTP (Press Through Pack) package having excellent gas barrier properties and transparency. <P>SOLUTION: In the PTP package, a bottom member 55 having a recessed part 51 for storing a content and a flange part 53, and a lid member 57 for sealing the recessed part 51 are heat-bonded to each heat seal layer. The heat seal layer of either the bottom member 55 and the lid member 57 has the easy-peel properties, and the lid member 57 has a cut 59 formed in the flange part 53 in a linear or dotted shape. The PTP package has excellent gas barrier properties and transparency, and is capable of ensuring the easy openability without considering the breaking strength or the like of a lid member film, and therefore, the selection range of the lid member can be extended. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a press-through pack package having high moisture resistance, high gas barrier properties, visibility, and excellent easy-openability.

  Press through pack packaging (hereinafter referred to as PTP packaging) is generally formed by forming a recess within 20 mm in depth by hot vacuum forming, hot pressure forming, hot vacuum forming, etc. Medicines and various foods such as tablets and capsules are stored in the recesses, and the openings of the recesses are sealed and packaged with aluminum foil, thin rigid plastic sheets or flexible films. It is often used for packaging. Some have used aluminum foil for both the lid and the bottom for the purpose of ensuring a higher moisture-proof function. However, if aluminum foil is used for both the lid and the bottom material, the contents cannot be visually inspected for contamination and chipping. Moreover, depending on the strength of the aluminum foil, the contents cannot be easily extruded, and the contents may be damaged during extrusion. On the other hand, when an aluminum foil is used as a cover material, the aluminum foil is easy to avoid, and there is a problem that if unnecessary force is applied to the concave portion, it is torn and the contents are exposed. From such a current situation, various developments for controlling openability have been made.

  For example, there is a proposal to use a plastic film as a lid material, but the plastic film has insufficient openability, and tablets and the like may be destroyed. Therefore, a lid for PTP packaging has been developed in which an aluminum foil is laminated on one side of a polyester film having a thickness of 3 to 25 μm and the polyester film is subjected to easy-cut processing (Patent Document 1). It is said that opening is made easy by easy cutting. In the example of Patent Document 1, a polyester film is supplied between a processing roll in which protrusions for scar processing are projected on a circumference rotating in the opposite direction at the same speed and a receiving roll having a smooth surface, and the entire surface of the film is supplied. There are fine holes. Even if micropores are formed in a 30 μm thick polyester film, the openability is not improved, and the 2.5 μm thick polyester film is frequently broken by the above micropores and laminated with aluminum foil. Although it is not possible, an example in which an aluminum foil is laminated on a polyester film having a thickness of 9 μm in which fine holes are formed is described as having good openability.

  Further, in the PTP packaging body in which the solid article is housed in the recess formed on the back surface of the molded sheet and the recess is sealed with the sealing film, the sealing film is formed by forming the inorganic oxide layer on the base film. There is also a PTP package characterized in that a cut is formed in at least a part of a portion corresponding to the concave portion of the base film (Patent Document 2). Since a gas barrier property was imparted by using a base film formed with an inorganic oxide layer as a sealing film, and a cut was formed in at least a part of the portion corresponding to the concave portion of the base film, It is said that it is possible to easily take out solid articles by pushing with fingers with moderate force of adults. In an example of Patent Document 2, a laser beam is used to penetrate the base sheet from the base sheet side to form a notch in a perforation, and a cross-shaped notch is formed at a location corresponding to the recess. Yes.

  Also, it is a PTP wrapping body made of a bottom material in which a storage part is formed, and a lid material made of an aluminum foil and a paper base material, and is easy for the bonding layer (hereinafter referred to as a sealing layer) between the bottom material and the lid material. There is also a package having a peel function (Patent Document 3). By keeping the sealing strength between the bottom material and the aluminum foil within a predetermined range, the stored item can be sealed and stored, and the lid member is prevented from tearing in the middle. In the Example of patent document 3, the paper base material which comprises the outermost layer of the cover material which bonded together the paper base material and the aluminum foil with the adhesive agent is provided with a cut with a carbon dioxide laser, and the package is manufactured.

  Furthermore, there is also a solid packaging body composed of a bottom material composed of a plastic film substrate, an aluminum foil, and a sealing layer, and a lid material composed of a plastic film, a transparent metal vapor deposition film layer, and a sealing layer (Patent Literature). 4). The conventional solid packaging body has a bottom made of a transparent plastic film and a lid made of an aluminum foil and a sealant. However, in order to ensure a moisture-proof function, it is necessary to have a multilayer of 5 layers or more. However, it is said that it is possible to provide a low-cost package without coating multiple times by replacing the lid and the bottom material.

Also, the lid sheet is thick so as to have a peelable strength from the container sheet, and the portion of the lid sheet corresponding to the container portion of the container sheet is thin so as to have the necessary breakability when the contents are extruded. There is also a processed PTP package (Patent Document 5). In consideration of the convenience of the user who takes out multiple items at a time, while maintaining the opening function in the press-through method, peels off the cover material sheet from the container sheet of the package to take out multiple items. It is a PTP package that adds an open-type function and allows the user to select a convenient way to take out stored items.
JP 2002-178450 A Japanese Patent Laid-Open No. 06-278768 JP 2003-63558 A JP 2007-217014 A JP 2007-197084 A

  PTP packaging chemically protects the contents by controlling water vapor permeability and oxygen permeability, and physically protects the contents by a predetermined shape and mechanical strength of the bottom material and the lid material. Visibility that can confirm an object, easy opening that can be opened with appropriate strength, and the like are required. If an aluminum foil is used as the cover material, the gas barrier property and the unsealing property are excellent, but if the bottom material is also aluminum, the visibility is lowered. Moreover, although the cover material for PTP packaging of patent document 1 is what laminated | stacked aluminum foil, a bottom material consists of polyester-type resin and gas barrier property is not enough.

  In addition, the PTP package described in Patent Document 2 uses a base film formed with an inorganic oxide layer as a lid, and cuts into a cross shape at a location corresponding to a recess formed in the bottom of the lid. It is considered that it is difficult to ensure gas barrier properties.

  Moreover, although the package body of patent document 3 uses the cover material which consists of a paper base material and aluminum foil, it adheres a paper base material and aluminum foil with an adhesive agent, and also heat seals to aluminum foil. Layers need to be formed and the process is complicated.

  In addition, after storing tablets and capsules, the PTP package is punched into a predetermined number of sheets and commercialized. In the punching device, since the punching process is performed with the bottom material facing up and the lid material facing down, the sliding material and mechanical strength of the lid material are required for efficient production. For this reason, it is preferable that a lid material capable of improving the production efficiency can be selected. However, for example, the solid package described in Patent Document 4 uses easy-cut polyethylene terephthalate as a heat seal layer for the lid material to facilitate opening, and is not considered regarding easy-openability. When a base film having a high mechanical strength is used, opening is difficult.

  Moreover, in patent document 5, in consideration of the convenience of the user who takes out several things at once, the function which takes out several things by peeling a cover material sheet from the sheet | seat for containers of a PTP package is added. However, such a peel-open method requires pinching the hook at one end of the lid with a finger, and may be inconvenient for elderly people who have difficulty in fine work.

In view of such a current situation, an object of the present invention is to provide a package that can be easily opened by a press-through method instead of a peel-open method.
Another object of the present invention is to provide a PTP package that has a wide selection range of constituent members of the lid material and is excellent in gas barrier properties and visibility.

  As a result of examining the PTP package in detail, the present invention, etc., if the heat seal layer of either the cover material or the bottom material is an easy peel and a notch is formed in the cover material portion corresponding to the flange portion of the bottom material In addition, it is possible to maintain a high gas barrier property even when both of the lid member and the bottom member are constituted by a gas barrier member, and easy opening and easy opening by easy peeling and the above-mentioned cutting, It is not limited to members, and members that make up the cover material can be selected widely, and visibility is ensured by configuring either the cover material or the bottom material with a transparent member, making it easy to inspect the contents. As a result, the present invention has been completed.

That is, the present invention is a press-through pack packaging body in which a bottom material having a recess for storing contents and a flange portion and a lid material for sealing the recess are heat-sealed with each heat seal layer. And
The heat seal layer of either the bottom material or the cover material has an easy peel property, and the cover material is formed with a cut formed in a linear or dotted shape in the flange portion. A press-through pack package is provided.

  In the PTP package of the present invention, since the heat seal layer of the lid or bottom material has easy peel properties and the notch is formed in the lid material portion corresponding to the flange portion of the bottom material, Easy openability can be ensured without considering breaking strength and the like, and the selection range of the lid material can be expanded.

In the PTP package of the present invention, since the notch is formed in the lid portion corresponding to the flange portion of the bottom material, a high gas barrier property can be secured together with easy opening.
Further, in the present invention, since the notch is formed in the flange portion, the lid material can be prevented from being broken due to vibration during product processing or transportation, which is likely to occur when the bottom material has a notch in the recess. Excellent storage.

  The PTP package of the present invention can ensure the visibility of the contents by configuring either the lid member or the bottom member with a transparent member, and is excellent in safety.

The first of the present invention is a press-through pack packaging body in which a bottom material having a recess for storing contents and a flange portion and a lid material for sealing the recess are heat-sealed with each heat seal layer. There,
The heat seal layer of either the bottom material or the cover material has an easy peel property, and the cover material is formed with a cut formed in a linear or dotted shape in the flange portion. A press-through pack package. Hereinafter, the PTP package of the present invention will be described in detail.

(1) Configuration of PTP Package As shown in FIG. 1A, the PTP package (50) of the present invention includes a bottom material (51) having a recess (51) for storing contents and a flange (53). 55) and a lid member (57) for sealing the concave portion (51) are press-through pack packages obtained by heat-sealing the respective heat seal layers, and the bottom member (55) or the lid member ( 57) The heat seal layer of any one of 57) has an easy peel property, and the lid member (57) has a notch (59) formed in the flange portion (53) in the form of a line or a dot. It is characterized by that. As shown in FIG.1 (b), the said notch (59) is formed in a flange part (53). However, in FIG. 1B, the outer periphery of the recess 51 is surrounded by a broken line, but is not limited thereto. For example, as shown in FIG. 1 (c), a mode in which straight cuts are made at intervals of 90 degrees on the outer periphery of the recess (51), and as shown in FIG. As shown in FIG. 1 (e), a method of forming a circular cut that makes a round of the outer periphery of the recess (51), or the like may be used.

  In the present invention, the notch (59) formed in the flange portion is preferably in the range of 1 to 3 mm from the end of the recess. If the thickness is less than 1 mm, the gas barrier property may be deteriorated, and if it exceeds 3 mm, the easy-openability may be inferior.

  In addition, although the bottom material which has a recessed part and a fringe part and the cover material which coat | covers the said recessed part are heat-seal | fused, the PTP package of this invention has such a PTP package, for example, 3 21 sheets with x7 connected, 10 pieces with 2x5 connected, and 6 pieces with 2x3 connected may be formed as one sheet.

(2) Configuration of lid and bottom material The lid material and bottom material of the present invention have an oxygen permeability of 1 cc / m ² · day · atm (at 23 ° C. × 90%) or less, more preferably 0.2 cc / m. ² · day · atm (at 23 ° C. × 90%) or less, and water vapor permeability is 1 g / m ² · day · atm (at 40 ° C. × 90%) or less, more preferably 0.2 g / m ² · It preferably has a gas barrier property of day · atm (at 40 ° C. × 90%) or less. This is because if the oxygen permeability and water vapor permeability are in the above ranges, the storage stability of the stored items is excellent due to the high gas barrier property.

  As such a lid material and a bottom material, for example, as shown in FIG. 2, a laminated film in which a gas barrier film (10), an adhesive resin layer (20), and a heat sealable film (30) are bonded is used. Can be used. As shown in FIG. 3, a gas barrier film (10) formed by forming a coating film (15) containing a gas barrier resin such as polyvinyl alcohol on a base film (13) is used as an adhesive resin layer (20). May be a gas barrier film adhered to the heat-sealable film (30). Furthermore, as shown in FIG. 4, a gas barrier film (13) comprising a base film (13), a vapor deposition film (14) obtained by vapor-depositing an organic silicon compound, a metal or a metal oxide, and a gas barrier coating film (16). 10) may be a gas barrier film adhered to the heat-sealable film (30) by the adhesive resin layer (20). This is because the gas barrier property is particularly excellent. Moreover, what laminated | stacked heat-sealable resin on the aluminum foil can also be used as a gas barrier film.

In the present invention, it is preferable to use a laminated material obtained by laminating at least an aluminum foil and a heat seal layer as the bottom material, and use a transparent multilayer film having excellent gas barrier properties as the lid material. That is, in order to ensure the visibility with which the contents can be easily inspected, a transparent member may be used for either the lid member or the bottom member. However, if a transparent gas barrier film is used for the bottom member, Although the gas barrier property may be lowered due to the formation, the gas barrier property can be maintained high when used as a lid. In addition, if a transparent gas barrier film is used for the lid, the unsealing property may be reduced. However, the heat seal layer of either the lid or the bottom is easy peel, and the lid corresponds to the flange of the bottom. If a notch is formed in the material portion, it is possible to easily perform opening with the easy peel and the notch while maintaining a high gas barrier property. Due to the ease of opening, the members constituting the lid material can be selected widely without being limited to the easily openable members. Furthermore, if the bottom material is a laminate of aluminum foil, a high level of gas barrier properties can be ensured by an aluminum foil that is excellent in light-shielding contents and inexpensive. Moreover, since a recessed part is comprised by silver white, it is excellent also in designability. From the above, a preferable lid material constituting the PTP package of the present invention is provided with, for example, a vapor deposition film formed by vapor-depositing an organic silicon compound, a metal, or a metal oxide on one surface of a base film, In general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 or more) M represents an integer of 1 or more, and n + m represents a valence of M.) and at least one alkoxide represented by the formula, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer Is a gas barrier laminated film provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method, and the bottom material is an aluminum film in which a heat seal layer is laminated on an aluminum foil. Laminated film The Since the gas barrier multilayer film constituting the lid material can form a printing layer on any layer, fine printing can be performed.

(3) Gas Barrier Film As the lid material and bottom material used in the present invention, those having a heat seal layer in the innermost layer and a gas barrier film laminated on any layer can be suitably used. Such a gas barrier film is described below.

(A) Gas barrier laminated film As a gas barrier film used in the present invention, a vapor deposition film formed by vapor-depositing an organic silicon compound, a metal or a metal oxide is provided on one surface of a base film, and a general film is formed on the vapor deposition film. Formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more. M represents an integer of 1 or more, and n + m represents a valence of M.), and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Further, a gas barrier laminated film provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method can also be used. The gas barrier coating film is formed by a polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and at least one alkoxide chemically reacting with each other to form a strong three-dimensional network composite polymer layer. The film acts synergistically, has excellent gas barrier properties that prevent permeation of oxygen, water vapor, and the like, and also has excellent hot water resistance.

(I) Base film As the base film constituting the gas barrier laminate film, mechanical and physical sufficient to provide a vapor-deposited film or gas barrier coating film formed by vapor-depositing an organic silicon compound, metal or metal oxide, It is preferable to use a resin film that has chemical strength, can withstand the conditions for forming the vapor deposition film, and can satisfactorily hold without impairing the properties of the vapor deposition film.

  Such base films include polyethylene resins, polypropylene resins, cyclic polyolefin resins, fluorine resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers ( ABS resin), polyvinyl chloride resin, fluororesin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin , Polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin , It can be used films composed of various resins other like. In particular, a film of a polypropylene resin, a polyester resin, or a polyamide resin is preferable.

  One or more of the above resins are used, and the resin is formed into a single layer using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. Or two or more types of resin formed into a multilayer film by co-extrusion or the like, or a mixture of two or more types of resin to form a film, and a tenter method or a tubular method, etc. Various resin films formed by stretching in the axial direction can be used.

In this invention, as a film thickness of a base film, about 6-100 micrometers, More preferably, about 9-50 micrometers is preferable.
(Ii) Surface treatment In the present invention, a deposited film is formed by vapor-depositing an organosilicon compound, a metal or a metal oxide on one surface of the above-mentioned base film. Also good. Thereby, the adhesiveness with the vapor deposition film or the gas barrier coating film can be improved.

  Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. That is, by performing in-line plasma treatment immediately before forming a deposited film formed by depositing an organosilicon compound, metal, or metal oxide by physical vapor deposition or chemical vapor deposition described later, It is possible to remove moisture and dust from the surface of the film and to perform surface treatment such as smoothing, activating, etc. the surface. Furthermore, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of the plasma output, the kind of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

(Iii) Vapor deposition film formed by vapor-depositing organosilicon compound, metal or metal oxide Examples of the vapor deposition film in the present invention include a chemical vapor deposition method, a physical vapor deposition method or a combination thereof, It can be produced by forming a single-layer film consisting of one layer of a vapor-deposited film obtained by vapor-depositing a metal or metal oxide, or a multilayer film or a composite film consisting of two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. As described above, a vapor deposition film such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

One example of a method for forming a deposited film by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 5 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.
In the present invention, the base film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film 201 is further fed at a predetermined speed via the auxiliary roll 224. Then, it is conveyed onto the circumferential surface of the cooling / electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The mixed gas composition for vapor deposition is supplied onto the substrate film 201 conveyed on the circumferential surface of the cooling / electrode drum 225, and plasma is generated and irradiated by glow discharge plasma 230 to form a vapor deposited film. . Next, when the base film 201 on which the vapor deposition film is formed as described above is wound around the winding roll 234 via the auxiliary roll 233, a vapor deposition film formed by vapor-depositing an organosilicon compound by plasma chemical vapor deposition is formed. Can do. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. When the base film is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film formed by depositing an organosilicon compound can be formed on the base film. In FIG. 5, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of the vapor deposition film formed by vapor-depositing the organosilicon compound obtained in this way is formed on the base film in the form of a thin film in the form of SiO _x while oxidizing the plasma-formed source gas with oxygen gas. Therefore, the deposited film is a dense continuous layer having a small gap and a high flexibility. Therefore, the barrier property of the deposited film is an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like. Compared with a deposited film of a product, it is much higher, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film is cleaned by SiO _X plasma and polar groups and free radicals are generated on the surface of the base film, the adhesion between the deposited film to be formed and the base film is high. It will be a thing. Further, the degree of vacuum at the time of forming the deposited film is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum when forming a vapor-deposited film of inorganic oxide such as silicon oxide is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, The vacuum state setting time can be shortened, the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is a base film. Is formed into a dense and flexible thin film, and is usually an oxidation represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In this invention, it is preferable that it is a vapor deposition film containing an organosilicate compound as said vapor deposition film. In addition to the above, the type, amount, etc. of the compound contained in the deposited film can be changed by changing the conditions of the deposition process. Under the present circumstances, as content which said compound contains in a vapor deposition film, it is 0.1 to 50%, Preferably it is 5 to 20%. If the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the vapor-deposited film will be insufficient, and scratches, cracks, etc. will easily occur due to bending, etc., and high barrier properties will be stabilized. On the other hand, it may be difficult to maintain, and if it exceeds 50%, the barrier property may be lowered.

  Furthermore, in the present invention, in the vapor deposition film obtained by vapor-depositing an organosilicon compound, it is preferable that the content of the compound decreases from the surface of the vapor deposition film in the depth direction. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the vapor deposition film, and on the other hand, at the interface with the base film, the content of the above compound is small, and thus the close adhesion between the base film and the vapor deposition film. Will be strong.

  In the present invention, the deposited film is formed in the depth direction using a surface analyzer such as an X-ray photoelectron spectrometer (XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above physical properties can be confirmed by analyzing by ion etching or the like and conducting elemental analysis of the deposited film.

  In the present invention, the thickness of the deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. The film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. As a means for changing the film thickness of the vapor deposition film, it can be performed by a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas or a method of slowing the vapor deposition rate. .

  In the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, metal or metal oxide may be not only one layer of the vapor deposition film but also a multilayer film in which two or more layers are laminated and used. The materials may be used alone or as a mixture of two or more thereof, and a vapor deposition film mixed with different materials may be formed.

  In the present invention, examples of the vapor deposition monomer gas such as an organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. Etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, a vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an organic silicon compound by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method, A vapor deposition film formed by vapor deposition of metal or metal oxide can be formed.

  Specifically, an organic silicon compound, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a raw material is a metal or metal Using an oxidation reaction vapor deposition method in which oxygen is introduced and oxidized to be deposited on one side of the base film, and further, a plasma assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma is used. A vapor deposition film can be formed. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method of forming a vapor deposition film by physical vapor deposition will be described with reference to FIG. 6 showing a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus.

  First, the base film 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 through the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum evaporation apparatus 241. The evaporation source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 201 guided on the cooled coating drum 246, and if necessary, An oxygen gas or the like is ejected from the oxygen gas outlet 249 and a vapor deposition film formed by depositing, for example, aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. When the base film 201 on which the deposited film is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, a deposited film can be formed by physical vapor deposition. First, a first-layer deposited film is formed by using the above-described winding-type vacuum deposition apparatus, and then a deposition film is further formed thereon, or the above-described winding-type vacuum deposition apparatus is connected in series. Then, the vapor deposition film may be continuously formed to form the vapor deposition film composed of two or more multilayer films.

The deposited film formed by depositing a metal or a metal oxide may basically be a thin film deposited with a metal oxide, such as silicon (Si), aluminum (Al), magnesium (Mg), Metal oxides such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) The deposited film can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. Generally, examples other than silicon (Si) and aluminum (Al) are poor. Therefore, in the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). It is a range. In addition, although the film thickness of the said vapor deposition film changes with kinds etc. of the metal to be used or a metal oxide, it can be arbitrarily selected within the range of 50 to 2000 mm, preferably 100 to 1000 mm, for example. Moreover, the vapor deposition film formed by vapor-depositing a metal or metal oxide is used as a metal or metal oxide to be used in one kind or a mixture of two or more kinds to constitute a vapor deposition film mixed with different materials. You can also.

Furthermore, in the present invention, for example, a composite film composed of two or more layers of different kinds of vapor-deposited films can be formed by using both physical vapor deposition and chemical vapor deposition.
As a composite film composed of two or more layers of the above-mentioned different kinds of vapor-deposited films, first, a chemical vapor deposition method is used on a base film, and it is dense and flexible and can relatively prevent the occurrence of cracks. A composite film comprising two or more layers is provided by providing a vapor deposition film obtained by vapor-depositing an organosilicon compound, and then providing a vapor deposition film obtained by vapor-depositing a metal or metal oxide by physical vapor deposition on the vapor deposition film. It is preferable to constitute a vapor deposition film composed of a film. Contrary to the above, on the base film, a vapor deposition film formed by vapor-depositing a metal or a metal oxide is first provided by a physical vapor deposition method, and then a dense film is formed by a chemical vapor deposition method. It is also possible to provide a vapor-deposited film made of a composite film composed of two or more layers by providing a vapor-deposited film formed by vapor-depositing an organosilicon compound that is rich in flexibility and can relatively prevent the occurrence of cracks.

(Iv) Gas barrier coating film The gas barrier coating film used in the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic having 1 to 8 carbon atoms). Represents a group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. It contains the above alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. A coating film made of a gas barrier composition, which is coated on the vapor deposition film on the base film to provide a coating film, and has a melting point of 20 to 180 ° C. and the base film. Heat treatment at the following temperature for 10 seconds to 10 minutes It can be formed.

  In addition, the gas barrier composition is applied onto the deposited film on the base film, and two or more coating films are stacked, at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film. You may heat-process for 10 seconds-10 minutes, and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films.

As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.
In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an 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₎ can be exemplified ₄ like.

In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an 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,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more.

  In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (iso-OC ₃ H ₇ ) ₄ , tetra n butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be exemplified.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-OC ₃ H ₇ ) ₄ , tetra-n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and others.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film is coated. This is not desirable.

  In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer.

  When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

  The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.

  In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  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 can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a gas barrier obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally crosslinked to form a porous polymer having a low density, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 to 500 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. Part by mass.

In the present invention, the gas barrier laminate film can be produced by the following method.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction.

  Next, the gas barrier composition is applied onto the deposited film on the base film by a conventional method and dried. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 20 ° C. to 180 ° C. and below the melting point of the base film, preferably at a temperature in the range of 50 ° C. to 160 ° C. for 10 seconds to 10 minutes. To process. Thereby, a barrier film in which one or two or more gas barrier coating films of the gas barrier composition are formed on the vapor deposition film can be produced.

  A barrier film obtained by using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a barrier film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, On the coating film, a gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied to form a second coating film, and when these composite layers are formed, the gas barrier properties after hydrothermal treatment It is possible to produce a barrier film with improved resistance.

  Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer is applied. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the barrier film.

The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide.
The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by the hydrolysis by the action of the sol-gel catalyst, and the hydrolysis products are dehydrated and polycondensed. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

このポリマーは、ＯＲ基（エトキシ基などのアルコキシ基）が、直鎖状のポリマーから分岐した形で有する。このＯＲ基は、存在する酸が触媒となって加水分解されてＯＨ基となり、ゾルゲル法触媒（塩基触媒）の働きにより、まず、ＯＨ基が、脱プロトン化し、次いで、重縮合が進行する。すなわち、このＯＨ基が、下記の式（Ｉ）に示されるポリビニルアルコール系樹脂、または、下記の式（ＩＩ）に示されるエチレン・ビニルアルコール共重合体と重縮合反応し、Ｓｉ−Ｏ−Ｓｉ結合を有する、例えば、下記の式（ＩＶ）に示される複合ポリマー、あるいは、下記の式（Ｖ）及び（ＶＩ）に示される共重合した複合ポリマーを生じると考えられる。

This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. The OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel catalyst (base catalyst), and then polycondensation proceeds. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

上記の反応は常温で進行し、ガスバリア性組成物は、調製中に粘度が増加する。このガスバリア性組成物を、基材フィルム上の前記蒸着膜の上に塗布し、加熱して溶媒および重縮合反応により生成したアルコールを除去すると重縮合反応が完結し、基材フィルム上の前記蒸着膜の上に透明な塗布膜が形成される。なお、上記の塗布膜を複数層積層する場合には、層間の塗布膜中の複合ポリマー同士も縮合し、層と層との間が強固に結合する。

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied onto the vapor deposition film on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and the vapor deposition on the base film is completed. A transparent coating film is formed on the film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the surface of the vapor deposition film in which the organic reactive group of the silane coupling agent or the hydroxyl group generated by hydrolysis deposits the organic silicon compound, metal or metal oxide on the base film. Since it bonds to the hydroxyl group of the base film, the adhesion between the substrate film or the surface of the vapor deposition film and the coating film is also good. Thus, in the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, a metal or a metal oxide and the gas barrier coating film are, for example, a chemical bond, a hydrogen bond, or a hydrolytic or co-condensation reaction. Since a coordination bond or the like is formed, the adhesion between the deposited film and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. 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 molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). Further, the hydroxyl group can be chemically bonded to the adhesive resin layer to form a strong laminated structure.

  Examples of the method for applying the gas barrier composition of the present invention include, for example, once by a roll coater such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator or the like. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times. Further, under a normal environment, 50 to 300 ° C., preferably The gas barrier coating film of the present invention is formed by performing condensation at a temperature of 70 to 200 ° C. by heating and drying for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. Can do.

(B) Polyvinyl alcohol In this invention, polyvinyl alcohol can be used suitably as a gas-barrier film which comprises a cover material. Although there is no restriction | limiting in the thickness of the gas-barrier film which consists of polyvinyl alcohol, Preferably it is 10-30 micrometers.

  On the other hand, although polyvinyl alcohol can be used as a single layer film, since it is a water-soluble polymer, it may be a laminated film in which a coating film made of polyvinyl alcohol is formed on a substrate film having excellent water resistance. As such a base film, the base film described in the section of the gas barrier laminate film can be preferably used. Thereby, water resistance is securable. In addition, the coating film which consists of polyvinyl alcohol becomes like this. Preferably it is 5-50 micrometers, More preferably, it is 10-30 micrometers. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

(C) Ethylene / vinyl alcohol copolymer In the present invention, an ethylene / vinyl alcohol copolymer can also be suitably used as the gas barrier film. Although there is no restriction | limiting in the thickness of the gas-barrier film which consists of an ethylene vinyl alcohol copolymer, Preferably it is 10-30 micrometers.

  On the other hand, the ethylene / vinyl alcohol copolymer can be used as a single layer film, but may be a laminated film in which a coating film made of an ethylene / vinyl alcohol copolymer is formed on a base film. As such a base film, the base film described in the section of the gas barrier laminate film can be preferably used. Thereby, the various characteristics according to a base film, such as a mechanical characteristic, can be improved. The coating film made of an ethylene / vinyl alcohol copolymer is preferably 1 to 10 μm, more preferably 2 to 5 μm. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

(D) Metal foil In this invention, metal foil, such as aluminum foil, can be used as a gas barrier film. Preferably, it is a soft one subjected to heat treatment. For example, a soft aluminum foil of A1N30 specified in JIS H4160 with a thickness of 6 to 50 μm, more preferably 7 to 30 μm is suitable. The aluminum foil may have a different thickness when used as a lid material or when used as a bottom material. In addition, other metals such as tin or tin oxide can also be used.

(4) Heat-sealable film As the heat-sealable film, there can be used polyolefin resins having various heat-seal properties that can be melted by heat and fused to each other, and the like. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene-acetic acid Vinyl copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, these Acid modified by modifying polyolefin resin such as metal pentene polymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid Polyolefin resin, polyvinyl acetate Le resins, poly (meth) acrylic resin, polyvinyl chloride resin, may be a resin other like. Among these, polypropylene is preferred when performing heat and pressure sterilization.

  Moreover, in this invention, it is preferable that the heat seal layer of either the said bottom material or a cover material has easy peel property. As such an easy peel heat seal layer, it is a cohesive exfoliation type consisting of a film in which random PP, PE, PS, etc. are blended (mixed) at a certain ratio, a film consisting of two or three layers by coextrusion, There are delamination type in which the adhesive strength between the support layer and the seal layer is adjusted to be low, and interfacial delamination type made of easy-adhesive resin such as EVA, which can be selected as appropriate considering the heat seal layer of the bottom material. . As such an easy peel heat seal layer, a product name “VMX” manufactured by Mitsubishi Chemical Corporation, which is a polyolefin polymer alloy chemically modified with a polymerizable vinyl monomer such as styrene, There are trade names “SMX PY-3000”, “SMX PY-4000”, “Y-03”, “Y-04”, “XR22FT”, manufactured by Tosoh Corporation, trade name “Melsen Film”, and the like. If either the bottom material or the lid material has easy peel properties, the opening is facilitated. As such an easy peel heat seal layer, the peel strength between the heat seal of the bottom material and the cover material is preferably 1 to 20 N / 15 mm, more preferably 3 to 10 N / 15 mm.

  The PTP package of the present invention uses an easy peel as the heat seal layer. However, as shown in FIG. 7 (a), the opening method for taking out the stored material is to press the contents from the bottom. As shown in FIG. 7 (b), it is characterized in that it is broken from the cut. It has been found that by using a heat seal layer having an easy peel property, it is easy to open even when the press-through method is used. Furthermore, by forming a notch in the cover material, it is possible to facilitate opening regardless of the mechanical strength of the base film, and the selection range of the base film can be expanded. In addition, as shown in FIG.7 (c), a general easy peel heat seal layer peels a cover material from a bottom material by using an easily peelable heat seal layer.

In the present invention, one or more of the above resins can be melt-extruded, and a film made of the resin can be laminated with an adhesive or the like to form a heat seal layer.
In the present invention, the thickness of the heat seal layer is about 5 to 200 μm, preferably about 10 to 100 μm.

(5) Printed layer In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the lid or bottom material. Examples of the printed pattern layer include a normal gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, and other ink compositions on the base film or gas barrier coating film. For example, gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods are used to form a desired printing pattern consisting of, for example, letters, figures, patterns, symbols, etc. This can be configured.

  Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used. In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used.

The print layer may be printed by surface printing or reverse printing of a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern, and may be full surface printing or partial printing.
(6) Primer layer In the present invention, for example, a primer is applied to the surface of the gas barrier coating film to form a primer layer, and then an adhesive layer for laminating is formed on the surface of the primer layer. In addition, a substrate such as a heat seal layer can be laminated using a dry laminate lamination method via an adhesive layer for laminating. By providing such a primer layer, the adhesion strength between the metal foil and gas barrier coating film and the adhesive layer for laminating, anchor coat layer, heat seal layer, etc. that can be laminated on it is improved, and the lamination strength is improved. Can be made. Further, a primer layer may be formed on the surface of the gas barrier coating film, and a printing layer may be formed thereon.

As a primer constituting the primer layer, a polyurethane resin, a polyester resin or the like is a main component of the vehicle, and a silane coupling agent 0.05 to 10% with respect to 1 to 30% by mass of the polyurethane resin or polyester resin. A primer composition containing a mass and preferably 0.1 to 5 mass%, a filler of 0.1 to 20 mass%, preferably 1 to 10 mass%, and additionally containing a solvent and a diluent is used. be able to. If necessary, the primer composition may further contain a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber, and other additives. In the present invention, the primer layer has a thickness of 0.1 to 10.0 g / m ² (dry state). The primer composition is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc., the coating film is dried to remove the solvent and diluent, and if necessary An aging process etc. can be performed and it can be set as a primer layer.

(7) Laminating adhesive In the present invention, when any two layers are laminated, they can be bonded by a dry laminating lamination method via a laminating adhesive.

  The adhesive for laminating comprises a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta ) Acrylic acid adhesive, chloroprene rubber, nitrile Beam, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

Although there is no limitation in the usage-amount of the adhesive agent for lamination, Generally, it is 0.1-10 g / m < ² > (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

(8) Anchor coat agent In the present invention, for example, when the heat seal layer is formed by extrusion, the heat seal layer can be formed on the primer layer via the anchor coat agent. Examples of the anchor coating agent to be used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide Acting, improving processability such as laminating and printing, avoiding the occurrence of cracks in the barrier thin film layer made of inorganic oxide, and tight adhesion between the barrier film and the heat seal layer And the occurrence of cracks in the barrier thin film layer made of an inorganic oxide can be prevented, and the laminate strength can be improved. The anchor coat agent layer made of the anchor coat agent preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

(9) Outer layer OP varnish or the like may be applied to the outermost layer on the lid or bottom material constituting the PTP package of the present invention.

(10) Manufacturing method of PTP package body The PTP package body of the present invention is prepared in advance with a lid material and a bottom material, the bottom material is molded to form a recess and a fringe portion, and contents such as tablets are placed in the recess. It can be manufactured by covering the lid material prepared in advance and heat-sealing the fringe part so that the innermost layer becomes a heat seal layer. The bottom material can be molded using a conventionally known PTP molding machine.

  In addition, for example, when 21 sheets of 3 × 7 are connected to each other, a perforation is made by a slitter engraving device so that the outer periphery of each concave portion can be separated, and then cut by sheet by a punching device. Good.

  The present invention is characterized in that a notch is formed at a location corresponding to the fringe portion of the lid material. However, a lid material in which a notch is previously formed at a predetermined position is used, and a bottom material formed with a recess is heat-sealed. The PTP package of the present invention can be manufactured. Moreover, the bottom material and lid material which shape | molded the recessed part are heat-seal | fused, Then, a notch can be formed in the location corresponding to the fringe part of a lid material at the time of cooling, and a PTP package body can also be manufactured. Further, after the perforation is made by the slitter marking device described above, the cover material corresponding to the fringe portion is cut and the PTP package of the present invention can be manufactured.

  The incision can be formed by laser beam irradiation or a press cutting blade. For example, when the cover material is cut in advance and then heat-sealed with the bottom material, the cut can be formed with a push cutting blade or the like. In addition, when the cut is formed after heat sealing between the lid member and the bottom material, the cut can be formed by laser beam irradiation or a push cutting blade. Furthermore, even when the cut is formed after the perforation is formed by the slitter marking device, the cut can be formed by laser beam irradiation or a push cutting blade.

  The depth of the cut can be selected depending on the thickness of the base film, the mechanical strength, and the like. However, when the cut is formed after the base material and the cover material are heat-sealed, the depth of the cut is made to penetrate the cover material. It is preferable to form an incision. In the present invention, since a gas barrier film having a high gas barrier property is used and a notch is formed in the flange portion, even if a notch penetrating the cover material is formed, the gas barrier property is not lowered and the easy-openability is reduced. This is because it can be secured.

  For the formation of the cut with the push cutting blade, a Thomson blade in which the blade is embedded in a plate or a pinnacle die in which the blade is formed with unevenness on a metal sheet can be suitably used.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.
Example 1
3 g / m ^{2 of} ester adhesive was applied to a polyethylene terephthalate film having a thickness of 16 μm, and an aluminum foil having a thickness of 30 μm was laminated. Next, 3 g / m ^{2 of} ester adhesive was applied to the aluminum foil, and an unstretched polypropylene film (trade name “P-1128” manufactured by Toyobo Co., Ltd.) having a thickness of 30 μm was laminated to the bottom material. Was prepared.

Also, 3 g / m ² of ester adhesive was applied to a 12 μm thick gas barrier film (trade name “IB-PET-PXB” manufactured by Dai Nippon Printing Co., Ltd.), and an easy peel heat seal (30 μm thick) Toray Film Processing Co., Ltd., trade name “9501-H”) was laminated to prepare a lid.

The bottom material was cut into a square of 50 mm in length and width, and a recess was formed to have a diameter of 11 mm and a height of 5 mm.
In addition, perforations were formed in the lid as shown in FIG. The perforation has a width of 0.1 mm, a length of 3 mm, and an interval of 1 mm, and a perforation that penetrates the lid material film with a pinnacle blade having an initial perforation using a press at a location 1 mm from the end of the recess. Formed.

  A tablet having a diameter of 9 mm and a thickness of 4 mm was accommodated in the bottom, and the lid was heat-sealed to produce a PTP package. The peel strength between the heat seal of the bottom material and the lid material of this PTP package was 9 N / 15 mm.

  8 (a), the recess is cut out as shown in FIG. 8 (b), the lid from which the recess is removed is inverted as shown in FIG. 8 (c), and the jig (90) is attached. Pressing was performed at a speed of 50 mm / min, and the unsealing property was evaluated. Visibility, oxygen permeability, and water vapor permeability were also measured. The results are shown in Table 1. The oxygen permeability was measured with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. The water vapor permeability was measured with a measuring instrument (model name, PERMATRAN 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH.

(Example 2)
An unstretched polypropylene film with a thickness of 200 μm (made by Idemitsu Techno Fine Co., Ltd., trade name “FG-104”) was coated with 3 g / m ^{2 of} an ester adhesive, and an EVOH film with a thickness of 30 μm (manufactured by Kuraray Co., Ltd.). , Product name “EF-XL”), and then 3 g / m ² of ester adhesive was applied to the EVOH film, and a 50 μm-thick unstretched polypropylene film (manufactured by Toray Film Processing Co., Ltd. Fan NO-3301 ") was laminated to prepare a bottom material.

Also, 3 g / m ^{2 of} ester adhesive was applied to 30 μm thick aluminum foil, and an easy peel heat seal (trade name “9501-H” manufactured by Toray Film Processing Co., Ltd.) with a thickness of 30 μm was laminated. A lid was prepared.

A PTP package was produced in the same manner as in Example 1 using the bottom material and the lid material. The peel strength between the heat seal of the bottom material and the lid material of this PTP package was 9 N / 15 mm.
Further, in the same manner as in Example 1, the unsealing property, visibility, oxygen permeability, and water vapor permeability were evaluated. The results are shown in Table 1.

(Comparative Example 1)
A heat sealant (Dainippon Ink Co., Ltd., A-100Z-5) was applied to a 20 μm thick aluminum foil to a thickness of 4 μm to prepare a lid.

  On the other hand, as the bottom material, PVC having a thickness of 250 μm (Mitsubishi Resin Co., Ltd., Vinyl foil C-850) was used, and the unsealing property, visibility and oxygen permeability were the same as in Example 1 except that no perforation was formed. The water vapor permeability was evaluated. The results are shown in Table 1.

(Comparative Example 2)
A heat sealant (A-811P, manufactured by Dainippon Ink Co., Ltd.) was applied to a 20 μm thick aluminum foil to a thickness of 4 μm to prepare a lid.

On the other hand, as the bottom material, PP having a thickness of 250 μm (Pureley, MG-20 manufactured by Idemitsu Petrochemical Co., Ltd.)
0) was used, and the unsealing property, visibility, oxygen permeability, and water vapor permeability were evaluated in the same manner as in Example 1 except that no perforation was formed. The results are shown in Table 1.

(Comparative Example 3)
3 ester adhesives on 16μm thick PET (Toray Film Processing Co., Ltd., F-865)
Apply g / m ² , laminate 30 μm thick aluminum foil, then apply 3 g / m ² ester adhesive to the aluminum foil, and 50 μm thick PP (Toray Film Co., Ltd. NO-3
301) was laminated to adjust the bottom material.

On the other hand, a heat sealing agent (Dainippon Ink Co., Ltd., A-811P) was applied to an aluminum foil having a thickness of 20 μm to prepare a lid.

  A PTP package was produced in the same manner as in Example 1 except that the bottom material and the lid material were used and no perforation was formed. Further, in the same manner as in Example 1, the unsealing property, visibility, oxygen permeability, and water vapor permeability were evaluated. The results are shown in Table 1.

  The PTP package of the present invention is a PTP package that has a wide selection range of base films and is excellent in gas barrier properties and transparency.

It is a figure explaining the PTP package of this invention. 1A is a cross-sectional view of a PTP package, FIG. 1B is a plan view, and FIGS. 1C to 1E are plan views for explaining the shape of a cut. FIG. 2 is a diagram for explaining the layer structure of the gas barrier film used in the present invention. FIG. 3 is a diagram for explaining the layer structure of the gas barrier film of the present invention, and shows a mode in which the gas barrier film is composed of a base film and a predetermined coating layer. FIG. 4 is a diagram for explaining the layer structure of the gas barrier film of the present invention. The gas barrier film comprises a base film, a deposited film obtained by depositing an organosilicon compound, metal or metal oxide, and a predetermined gas barrier property. It is a figure which shows the aspect which consists of a coating film. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus. It is a figure explaining the opening by a press through system and a peel open system. In the Example of this invention, it is a figure explaining the method of evaluating openability.

Explanation of symbols

10 ... gas barrier film,
13 ... Base film,
14 ... Vapor deposition layer formed by vapor-depositing an organosilicon compound, metal or metal oxide,
15 ... coating film,
16 ... Gas barrier coating film,
20: Adhesive resin layer,
30 ... Heat-sealable film

Claims (5)

A press-through pack packaging body in which a bottom material having a concave portion for storing contents and a flange portion, and a lid member for sealing the concave portion are heat-sealed with each heat seal layer,
The heat seal layer of either the bottom material or the cover material has an easy peel property, and the cover material is formed with a cut formed in a linear or dotted shape in the flange portion. , Press-through pack packaging. The bottom material and the lid material have an oxygen permeability of 1 cc / m ² · day · atm (at 23 ° C. × 90%) or less and a water vapor permeability of 1 g / m ² · day · atm (at 40 ° C. × 90%) or less, the press-through pack package according to claim 1.   The press-through pack package according to claim 1 or 2, wherein at least one of the bottom member and the cover member has transparency.   The press-through pack package according to any one of claims 1 to 3, wherein the bottom material includes a base film layer, a metal foil layer, and a heat seal layer. The lid material is provided with a vapor deposition film formed by vapor-depositing an organic silicon compound, a metal or a metal oxide on one surface of a base film, and the general formula R ¹ _n M (OR ² ) _m (however, In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, n + m represents the valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further polycondensed by a sol-gel method. The press-through pack package according to any one of claims 1 to 4, which is a gas barrier laminated film provided with a gas barrier coating film made of a gas barrier composition obtained in this manner.

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