JP2009040439A - Oxygen moisture absorbing pouch and packaged product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen moisture absorbing pouch having high gas barrier properties to oxygen, steam or the like, having a high catching function to oxygen and moisture existing or generated in the packaging pouch, and excellent as a pouch for storing an electronic component or the like. <P>SOLUTION: The oxygen water moisture pouch uses a moisture absorbing laminated body and an oxygen absorbing laminated body. The moisture absorbing laminated body (a) consists of a moisture absorbing resin film comprising a resin composition including a substrate film (i), a barrier thin film layer (ii) and a drying agent (iii). The oxygen absorbing laminated body (b) consists of an oxygen absorbing resin film comprising a resin composition including a substrate film (i), a barrier thin film layer (ii), an oxidative resin (iii) and the like. The bag is manufactured so that (c) the moisture absorbing resin film faces the oxygen absorbing resin film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an oxygen-moisture absorbing pouch and a packaged product using the same. More specifically, the present invention prevents oxygen gas and water vapor from permeating, has excellent barrier properties, captures oxygen and moisture present or generated in the pouch, and protects the quality of the contents. The present invention relates to an oxygen-water-absorbing pouch having a barrier property useful for packaging and a packaged product using the same.

  Conventionally, materials such as plastic films, paper base materials, metal foils or vapor-deposited films thereof are used, and any combination of these materials is used to produce packaging materials having various layer configurations, which are then used for packaging bags. A plastic packaging made of various forms filled with packaging and packaging of various foods and drinks, chemical products such as liquid detergents, cosmetics, pharmaceuticals, miscellaneous goods, industrial materials, etc. Products have been developed and proposed.

In the packaging material constituting the plastic packaging product described above, from the viewpoint of protecting the quality of the contents, extending the storage period, etc., it is excellent in heat sealability and can sufficiently satisfy the sealability and consumption. Sometimes it is required to have an easy-open property that allows the packaging bag to be easily opened. In addition, the packaging material constituting the plastic packaging product described above has a gas barrier property that prevents permeation of oxygen gas, water vapor, etc., depending on the contents to be filled and packaged, or the odor of the contents. It is also required to have a fragrance retaining property that protects and the like. Further, the packaging material constituting the plastic packaging product is also required to have a light shielding property or a light shielding property for preventing the transmission of sunlight, fluorescent light, and the like.
Therefore, in recent years, various materials, materials, etc. have been used to develop packaging materials having various layer configurations, and accordingly, packaging bags, packaging products, etc. having various forms have been developed and proposed. Yes.

In recent years, for example, various packaging articles as containers that prevent oxidation of the contents of a container by removing oxygen in the container and preventing oxygen from entering the container from outside the container. Is provided.
For example, Patent Document 1 discloses a film comprising an oxygen scavenging composition comprising a polymer main chain, a cyclic olefin pendant group, a linking group for binding the olefin pendant group to the main chain, and a transition metal catalyst, and the oxygen scavenging composition. The multilayer film etc. which combined another layer with the film which becomes are shown.
However, a laminated body in which a polyethylene terephthalate film, which is widely used as a base material, is laminated on a film made of the oxygen scavenging composition described in Patent Document 1, and a packaged product is produced using it to produce ultraviolet light. Irradiation and oxygen absorption ability were evaluated. Polyethylene terephthalate shows absorption from around 350 nm, which is near ultraviolet light. Therefore, sufficient intensity of ultraviolet light does not reach the film made of oxygen scavenging composition, and oxygen absorption ability It has been found that this is not fully exhibited. Furthermore, since the film using the oxygen scavenging composition described in Patent Document 1 does not absorb moisture at all, there is a concern that performance deterioration may occur due to oxygen or moisture in electronic parts, electronic devices, electronic equipment, printed boards, and the like. There was a problem that it could not be used for storage of things.

Furthermore, Patent Document 2 describes a packaged product using an oxygen-absorbing resin film made of a resin composition containing an oxidizing resin film and a transition metal catalyst. In the production of the packaged product described in Patent Document 2, since the ultraviolet light is irradiated to the inner surface of the packaging body before and after filling and packaging of the product, the packaged product is used as a base film to be used. It has an advantage of exhibiting a stable oxygen absorption ability without depending on properties.
However, the packaging container described in Patent Document 2 also has a problem that it does not absorb moisture at all.
Special table 2003-521552 gazette JP 2006-291087 A

As mentioned above, especially for packaging pouches that preserve the contents whose performance is likely to be deteriorated due to oxygen and moisture, such as electronic parts, electronic devices, electronic equipment, printed boards, etc., the permeation of oxygen, water vapor, etc. from the outside While it is desired to have a function of preventing and collecting oxygen and moisture present or generated in the packaging pouch, no pouch having such characteristics has been obtained.
On the other hand, the present invention has a high gas barrier property against oxygen, water vapor, etc., and also has a high collection function for oxygen and moisture present or generated in the packaging pouch, and it is an electronic component, electronic device, electronic The present invention provides an oxygen-water-absorbing pouch that is particularly excellent as a storage pouch for contents that are liable to be deteriorated in performance due to oxygen and moisture, such as equipment and printed circuit boards.

  As a result of earnest research to improve the above problems, the present inventor used a resin composition mixed with a desiccant as a part of the layered material constituting the pouch, and an oxidizing resin in another layer. In addition, by using a resin composition containing a transition metal catalyst, it is possible to satisfactorily absorb oxygen and moisture present or generated in the pouch, and further, as a part of the laminated material constituting the pouch, barrier properties By providing a thin film layer or gas barrier coating film, it is possible to prevent the penetration of oxygen and water vapor from the outside, and in particular, it should be a pouch excellent in storage of electronic parts, electronic devices, electronic equipment, printed boards, etc. The headline and the present invention were completed.

That is, the present invention includes the following inventions (a) to (e).
(I) An oxygen moisture absorbing pouch using a moisture absorbing laminate and an oxygen absorbing laminate,
a) the moisture-absorbing laminate comprises a moisture-absorbing resin film comprising a resin composition containing (i) a base film, (ii) a barrier thin film layer, and (iii) a desiccant,
b) The oxygen-absorbing laminate comprises an oxygen-absorbing resin film comprising (i) a base film, (ii) a barrier thin film layer, and (iii) a resin composition containing an oxidizing resin and a transition metal catalyst. And c) an oxygen-moisture-absorbing pouch, wherein the bag is formed so that the moisture-absorbing resin film surface and the oxygen-absorbing resin film surface face each other.
(B) an oxygen moisture absorbing pouch using an oxygen moisture absorbing laminate comprising a base film, a barrier thin film layer, and an oxygen moisture absorbing resin film,
The oxygen moisture-absorbing resin film comprises a heat-sealable resin layer made of a resin composition containing a thermoplastic resin as a main component of a vehicle, an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, and a desiccant. An oxygen moisture-absorbing pouch comprising three layers in which a moisture-absorbing resin layer comprising a resin composition containing a thermoplastic resin as a main component of a vehicle is laminated in order.
(C) The barrier thin film layer comprises an organic silicon oxide vapor-deposited film by chemical vapor deposition or an inorganic oxide vapor-deposited film by vacuum vapor deposition. Oxygen moisture-absorbing pouch.
(D) an oxygen-moisture-absorbing pouch with a gas barrier coating film provided on the barrier thin film layer,
The gas barrier coating film has a general formula R ¹ _n M (OR ₂ ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, 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), a polyvinyl alcohol-based resin and / or ethylene. A gas barrier composition comprising a vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent (a) The oxygen-moisture-absorbing pouch according to any one of to (c).
(E) Before filling the oxygen water-absorbing pouch according to any one of (i) to (d) with the contents, after filling, or simultaneously with filling, the inner surface of the pouch is irradiated with ultraviolet rays, A packaged product that is hermetically sealed by heat-sealing the opening.

The oxygen-moisture-absorbing pouch of the present invention can absorb oxygen and moisture that are present or generated in the pouch well, and can prevent the transmission of oxygen and water vapor from the outside. It is possible to stably store the contents of which the performance is likely to be deteriorated due to oxygen and moisture such as devices and printed boards over a long period of time.
Furthermore, the oxygen moisture-absorbing pouch of the present invention can reduce the volume of the packaged product because there is no need to put a pouch or the like containing another desiccant or oxygen absorber into the pouch, and the pouch or the like. It is possible to prevent the pouch from being damaged due to the above. That is, the oxygen-moisture-absorbing pouch of the present invention has an advantage that the contents are excellent in transportation and storage suitability.
In the present invention, when a gas barrier coating film is further provided on the barrier thin film layer, the gas barrier property against oxygen, water vapor, etc. can be remarkably improved.

The oxygen moisture absorbing pouch of the present invention will be described in detail with reference to the drawings.
1-3 is a schematic cross-sectional view showing an example of the layer structure of the moisture-absorbing laminate constituting the oxygen-moisture-absorbing pouch of the present invention, and FIG. 4 shows the oxygen-water-absorbing pouch of the present invention. FIG. 5 is a schematic cross-sectional view showing an example of the layer configuration of the oxygen-absorbing laminate, and FIG. 5 is a schematic diagram showing an example of the layer configuration of the oxygen-moisture-absorbing laminate constituting the oxygen-moisture-absorbing pouch of the present invention. FIG. 6 is a schematic perspective view showing an example of the configuration of the oxygen-moisture-absorbing pouch of the present invention produced by bag-making the laminate shown in FIGS. 1 and 4, and FIG. FIG. 8 is a schematic perspective view showing an example of a packaged product in which the oxygen moisture-absorbing pouch of the present invention shown in FIG.

First, to describe the water absorption laminated body constituting the oxygen-moisture absorbing pouch of the present invention, the water absorption laminate A ₁ constituting the oxygen-moisture absorbing pouch of the present invention, for example, as shown in FIG. 1 Further, a water-absorbing resin film 3 and a heat-sealable resin film made of a resin composition containing a desiccant are provided on one surface of the base film 1, and the barrier thin film layer further includes a desiccant. 4 can be illustrated as an example. As another example of the moisture-absorbing laminate, as shown in FIG. 2, a resin composition containing a desiccant and a resin composition containing a thermoplastic resin as a main component of a vehicle are used. A water-absorbing resin film 3 comprising a two-layer co-extrusion multilayer laminated film 5 in which these are co-extruded and laminated, and the water-absorbing resin layer 3a and the heat-sealable resin layer 3b are sequentially laminated. An example is a moisture-absorbing laminate A ₂ having a laminated structure provided on the barrier thin film layer 2 on the base film 1 so that 3a and the barrier thin film layer 2 are in contact with each other. Further, with regard to the above moisture-absorbing laminate, as shown in FIG. 3, using a resin composition containing a desiccant and a resin composition containing a thermoplastic resin as a main component of a vehicle, as shown in FIG. A water-absorbing resin film comprising a three-layer coextrusion multilayer laminated film 6 in which these are coextruded and laminated, and the heat-sealable resin layer 3b, the moisture-absorbing resin layer 3a, and the heat-sealable resin layer 3b ′ are sequentially laminated. An example is a moisture-absorbing laminate A ₃ having a laminated structure provided on the barrier thin film layer 2 on the base film 1.

  Further, the oxygen-absorbing laminate constituting the oxygen-moisture-absorbing pouch of the present invention will be described. The oxygen-absorbing laminate B constituting the oxygen-moisture-absorbing pouch of the present invention is, for example, as shown in FIG. An oxygen-absorbing resin film 7 comprising a resin composition containing a barrier thin film layer 2 on one surface of the base film 1 and further containing an oxidizing resin and a transition metal catalyst in the barrier thin film layer and heat sealing The laminated structure which provided the conductive resin film 4 in order can be illustrated. Although not shown, the oxygen-absorbing resin film has a two-layer coextrusion multilayer laminated film structure in which an oxygen-absorbing resin layer and a heat-sealable resin layer are sequentially laminated, A three-layer coextrusion multilayer laminated film structure in which a water-soluble resin layer, an oxygen-absorbing resin layer, and a heat-sealable resin layer are laminated in order, and these oxygen-absorbing resin films are the water-absorbing resin films described above. Similarly to the above, the barrier thin film layer 2 on the base film 1 is provided.

  Further, the oxygen moisture absorbing laminate constituting the oxygen moisture absorbing pouch of the present invention will be described. The oxygen moisture absorbing laminate C constituting the oxygen moisture absorbing pouch of the present invention is, for example, as shown in FIG. In addition, a barrier thin film layer 2 is provided on one surface of the base film 1, and the barrier thin film layer further includes a heat sealable resin film 4, an oxidizing resin, and a transition metal catalyst. The laminated structure which provided the moisture-absorbing resin film 3 which consists of the oxygen-absorbing-resin film 7 and the resin composition containing a desiccant can be illustrated.

The above illustrations illustrate a few examples of the layer structure of the laminate constituting the oxygen-moisture-absorbing pouch of the present invention, and it goes without saying that the present invention is not limited thereby. Absent. For example, in the above-described moisture-absorbing laminate A ₁ and oxygen-absorbing laminate B, when the moisture-absorbing resin film 3 and the oxygen-absorbing resin film 7 have heat sealing performance, the above heat-sealable resin layer However, it is not always necessary to provide a heat-sealable resin film. Further, in the above, an example in which a barrier thin film layer is provided on a base material and a moisture absorbing resin film is provided on the barrier thin film layer has been described. However, a barrier thin film layer is provided on a moisture absorbing resin film or the like. Needless to say, a substrate may be provided thereon.

Next, the structure of the oxygen moisture absorbing pouch of the present invention using the moisture absorbing laminate or the oxygen absorbing laminate will be described. As such an oxygen moisture absorbing pouch, for example, as shown in FIG. The moisture-absorbing laminate A ₁ and the oxygen-absorbing laminate B are prepared, and the heat-sealable resin films 4 and 4 located in the innermost layer are overlapped with each other, and then the outer periphery of the outer periphery The three sides of the end are heat-sealed to form the heat-sealed portions 11, 11, and 11 and the opening 12 is formed to produce a three-side-sealed oxygen moisture absorbing pouch D.

  In the present invention, as shown in FIG. 7, the oxygen moisture absorbing pouch D of the present invention manufactured as described above is used, and, for example, the ultraviolet irradiation device 13 is indicated by an arrow P from the opening 12. The oxygen water absorbing pouch D is moved up and down to irradiate the inner surface of the oxygen moisture absorbing pouch D with ultraviolet light 14 and then irradiated with the ultraviolet light 14 as shown in FIG. In addition, from the opening 12, for example, the content 15 such as an electronic component, an electronic device, an electronic device, and a printed board is filled, and then the opening 12 is heat-sealed to form an upper seal portion 16. The packaged product E of the present invention using the oxygen moisture-absorbing pouch D of the present invention can be produced.

Although not shown, the oxygen moisture absorbing pouch may be provided with an opening notch such as an I notch or a V notch. The above illustrations are examples of the oxygen-moisture-absorbing pouch and packaged product of the present invention, and the present invention is not limited thereto. For example, as the form of the packaging bag of the present invention Although not shown, for example, oxygen water-absorbing pouches having various forms such as a pillow packaging form, a gusset packaging form, and a standing (self-supporting) pouch packaging form can be manufactured.
Moreover, although not shown in figure, the oxygen moisture absorption laminated body shown in said FIG. 5 can be used, and the oxygen moisture absorption pouch and package product of this invention which consist of various forms can be manufactured similarly to the above. Furthermore, with respect to the irradiation of ultraviolet light, for example, the state of the raw film before bag making, the packaging bag before filling the contents, the packaging bag after filling, or the packing bag at the same time as filling, the ultraviolet ray is irradiated. Light can be irradiated.

Next, the material, the manufacturing method, etc. which comprise the oxygen moisture absorption pouch etc. of this invention are demonstrated. 1. Base film As a base film for forming the oxygen moisture-absorbing pouch and the like of the present invention, this is a basic material such as a moisture-absorbing laminate and an oxygen-absorbing laminate constituting the oxygen and moisture absorbing pouch of the present invention. Therefore, it has excellent properties in mechanical, physical, chemical, etc., in particular, has strength and toughness, and has heat resistance, and further, an inorganic oxide deposited film. In addition, since a gas barrier coating film or the like may be formed, a resin film that can withstand the formation conditions and satisfy the conditions such as being able to hold them satisfactorily without impairing the characteristics, or Use a sheet.

  Specifically, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene. Copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyamide resins such as various nylons , Polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cell It can be used films or sheets of various resins such as over scan resins. In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

As the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used to form a film such as an extrusion method, a cast molding method, a T-die method, a cutting method, and an inflation method. A method of forming a film of each of the above-mentioned various resins alone, or a method of forming a multi-layer coextrusion film using two or more of various resins, Used to produce various resin films or sheets by mixing and forming a film before forming a film, and if necessary, for example, using a tenter method or a tubular method Thus, various resin films or sheets formed by stretching in a uniaxial or biaxial direction can be used.
In the present invention, the film thickness of various resin films or sheets is preferably 6 to 100 μm, more preferably 9 to 50 μm.

It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness In addition, various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. A very small amount to several tens of percent can be arbitrarily added depending on the purpose.
In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Etc. can be arbitrarily used, and further, a modifying resin or the like can also be used.

Further, in the present invention, the surface of the above-described various resin films or sheets on which the barrier thin film layer is provided is provided in advance as necessary in order to improve the tight adhesion with the barrier thin film layer described later. A desired surface treatment layer can be provided.
As the surface treatment layer, 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, etc. is optional. For example, a corona discharge treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer and the like can be formed and provided.

The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and a barrier thin film to be described later, but as a method for improving the above close adhesion. For example, on the surface of various resin films or sheets, in advance, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, an adhesive layer, or a deposition anchor coating agent layer is arbitrarily formed, It can also be a surface treatment layer.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition comprising a main component of a vehicle such as a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

2. Barrier thin film layer Next, the barrier thin film layer constituting the moisture-absorbing laminate or oxygen-absorbing laminate in the oxygen-moisture-absorbing pouch of the present invention will be described. The barrier thin film layer can be formed of a vapor-deposited film of an inorganic oxide by chemical vapor deposition or physical vapor deposition.

(1) Formation of vapor-deposited film by chemical vapor deposition As chemical vapor deposition, specifically, for example, chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. An inorganic oxide vapor-deposited film can be formed using a phase growth method (chemical vapor deposition method, CVD method).
More specifically, on one surface of the base film, moisture-absorbing resin film, oxygen-absorbing resin film, or oxygen-absorbing resin film, an evaporation monomer gas such as an organic silicon compound is used as a raw material, and carrier gas is argon. Vapor deposition of inorganic oxides such as silicon oxide using low temperature plasma chemical vapor deposition method using inert gas such as gas, helium gas, oxygen as supply gas and using low temperature plasma generator etc. A film can be formed.
In the above, as the low-temperature plasma generator, for example, generators such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, but in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

Specifically, an example of the method for forming a vapor-deposited film of an inorganic oxide by the plasma chemical vapor deposition method will be described. FIG. 9 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing the outline of the method for forming a vapor-deposited film of an inorganic oxide by the plasma chemical vapor deposition method.
As shown in FIG. 9, in this invention, the base film 1 etc. are unwound from the unwinding roll 23 arrange | positioned in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21, and also the base film 1 etc. Then, it is conveyed on the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed.

  In the present invention, vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound or the like is supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and a mixed gas composition for vapor deposition composed thereof is prepared. Then, the vapor mixture gas composition is introduced into the vacuum chamber 22 through the raw material supply nozzle 29, and glow discharge is performed on the substrate film 1 and the like conveyed on the cooling / electrode drum 25 peripheral surface. Plasma is generated by plasma and irradiated to form a deposited film of an inorganic oxide such as silicon oxide to form a film.

In the present invention, a predetermined power is applied to the cooling / electrode drum 25 from the power supply 31 arranged outside the chamber at that time, and a magnet 32 is provided in the vicinity of the cooling / electrode drum 25. Arrangement is promoted to generate plasma. Next, the base film 1 or the like on which the inorganic oxide vapor deposition film such as silicon oxide is formed is wound around the take-up roll 34 via the guide roll 33, and the base film 1 having the inorganic oxide vapor deposition film is obtained. Etc. can be manufactured.
The above exemplification is an example, and the present invention is not limited thereby.

In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one kind of material is used. Alternatively, it is also possible to form a vapor-deposited film of an inorganic oxide that is used in a mixture of two or more kinds and mixed with different materials.
In the above, the inside of the vacuum chamber is depressurized by a vacuum pump, and the degree of vacuum is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁸ mbar, preferably, the degree of vacuum is 1.33 × 10 ^{−3 to} 1.33 × 10. It is preferable to adjust to ^-7 mbar.

In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber via the raw material supply nozzle. Introduce in.
In this case, the content of the organosilicon compound in the mixed gas can be 1 to 40%, the content of oxygen gas can be 10 to 70%, and the content of inert gas can be 10 to 60%. The mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be 1: 6: 5 to 1:17:14.

On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the electrode, 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 plasma is derived from one or more gas components in the mixed gas. In this state, the base film or the like is conveyed at a constant speed, and the substrate on the cooling / electrode drum peripheral surface is transferred by glow discharge plasma. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on a material film or the like.
The degree of vacuum in the vacuum chamber at this time is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁴ mbar, preferably 1.33 × 10 ^{−1 to} 1.33 × 10 ^−2. It is preferable to adjust to mbar, and the conveyance speed of the substrate film or the like is preferably adjusted to 10 to 300 m / min, and preferably 50 to 150 m / min.

  In the plasma chemical vapor deposition apparatus described above, an inorganic oxide vapor deposition film such as silicon oxide is formed in the form of SiOx while oxidizing a plasma source gas with oxygen gas on a substrate film or the like. Since it is formed in a thin film shape, the formed vapor-deposited film of inorganic oxide such as silicon oxide is a continuous layer that is dense and has few gaps and is highly flexible. Therefore, the gas barrier property of the vapor-deposited film of inorganic oxide such as silicon oxide is much higher than that of the vapor-deposited film of inorganic oxide such as silicon oxide formed by the conventional vacuum vapor deposition method or the like. Can provide sufficient gas barrier properties.

In the present invention, the surface of the base film or the like is cleaned by the SiOx plasma, and polar groups, free radicals, etc. are generated on the surface of the base film or the like. This has the advantage that the tight adhesion between the oxide deposition film and the base film is high.
Furthermore, as described above, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁴ mbar, preferably 1.33 × 10 ^{−. Since} it is adjusted to ^{1 to} 1.33 × 10 ⁻² mbar, it is compared with the degree of vacuum (1.33 × 10 ^{−4 to} 1.33 × 10 ⁻⁵ mbar) when forming a deposited film by the conventional vacuum deposition method. Since the degree of vacuum is low, it is possible to shorten the time for setting the vacuum state when the base film is exchanged, the degree of vacuum is stabilized, and the film forming process is stabilized.

In the present invention, a vapor deposition film of silicon oxide 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 It is closely bonded to one surface of a base film and the like to form a dense, flexible thin film, and is generally represented by a general formula: SiOx (wherein x represents a number of 0 to 2). It is a continuous thin film mainly composed of silicon oxide.
As the above-described silicon oxide vapor deposition film, silicon oxide vapor deposition represented by the general formula: SiOx (wherein x represents the number of 1.3 to 1.9) is required from the viewpoint of transparency and barrier properties. A thin film mainly composed of a film is preferable.
In the above, the value of x varies depending on the molar ratio of vapor deposition monomer gas to oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of x decreases, but the film itself is yellow. It becomes sexual and becomes less transparent.

  The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of carbon, hydrogen, silicon or oxygen, or at least one compound composed of two or more kinds of elements is chemically chemistry. It is preferably contained by bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, an organic silicon compound as a raw material or a derivative thereof is further added. It may be contained by a chemical bond or the like.

Specific examples 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 addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.
As a content rate which said compound contains in the vapor deposition film | membrane of a silicon oxide, 0.1 to 50%, Preferably, 5 to 20% is preferable.
In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. easily occur due to bending, It becomes difficult to stably maintain a high barrier property, and if it exceeds 50%, the gas barrier property is lowered, which is not preferable.

  Further, in the present invention, in the silicon oxide vapor-deposited film, the content of the above compound is preferably decreased from the surface of the silicon oxide vapor-deposited film in the depth direction, whereby the silicon oxide vapor-deposited film is formed. On the surface of the film, impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the base material, close adhesion between the base film and the silicon oxide vapor deposition film is possible. Will be strong.

  In the present invention, for the above-described deposited film of silicon oxide, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) is used. The physical properties as described above can be confirmed by performing elemental analysis of the deposited film of silicon oxide using a method of analysis by ion etching in the depth direction.

Further, in the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably 50 to 4000 mm, and specifically, the film thickness is preferably 100 to 1000 mm. If the thickness is more than 1000 mm, and more than 4000 mm, cracks and the like are likely to occur in the film, which is not preferable. If the thickness is less than 100 mm, and less than 50 mm, the gas barrier effect cannot be expected.
The film thickness of the deposited film can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.
In addition, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas or the method of slowing the vaporization rate. Etc.

In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyl Trimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane , Methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used.
Among the organosilicon compounds as described above, 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane is used as a raw material because of its handleability and the characteristics of the formed continuous film. Is particularly preferred.
Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

(2) Formation of Vapor Deposition Film by Physical Vapor Deposition Method In the present invention, the inorganic oxide vapor deposition film may be a physical layer such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. It can be formed using a phase growth method (Physical Vapor Deposition method, PVD method).
Specifically, using a metal oxide as a raw material, a vacuum deposition method in which the metal oxide is heated and deposited on a base film, a moisture absorbing resin film, an oxygen absorbing resin film, or an oxygen moisture absorbing resin film, Or, use a metal or metal oxide as a raw material, oxidize by introducing oxygen to oxidize and deposit it on a substrate film, etc., and plasma-assisted oxidation that assists the oxidation reaction with plasma An amorphous thin film of an inorganic oxide can be formed using a reactive vapor deposition method or the like.
In the above, the heating method of the vapor deposition material can be performed by, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like.
Examples of the deposited film of the inorganic oxide include a deposited film of a metal oxide. Specifically, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K ), Tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. it can. Preferable examples include metals such as silicon (Si) and aluminum (Al).

The deposited metal oxide film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide. The notation can be expressed by, for example, MOx such as SiOx, AlOx, and MgOx. (In the formula, M represents a metal element, and the value of x varies depending on the metal element).
Moreover, as a range of said value of x, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0-1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1.5 for boron (B), 0 to 2 for titanium (Ti). Lead (Pb) can take values in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.
In the above, when x = 0, it is a perfect metal and cannot be used because it is not transparent. In addition, the upper limit of the range of x is a completely oxidized value.
In the present invention, silicon (Si) and aluminum (Al) are preferably used, and silicon (Si) has a value in the range of 1.0 to 2.0, and aluminum (Al) has a value in the range of 0.5 to 1.5. Things can be used.

In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the metal used or the type of metal oxide, but is, for example, 50 to 4000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
In the present invention, the inorganic oxide vapor-deposited film is a metal to be used, or the metal oxide is one or a mixture of two or more, and mixed with different materials. It is also possible to constitute a vapor deposition film.

Next, in the present invention, a method for forming a vapor-deposited film of the above inorganic oxide will be described. FIG. 10 is a schematic configuration diagram illustrating an example of a take-up vacuum deposition apparatus.
As shown in FIG. 10, in the take-up chamber 41 of the take-up type vacuum vapor deposition apparatus 40, the base film 1 and the like fed out from the take-out roll 42 are cooled through the guide rolls 43 and 44, and the cooled coating drum 45. Be guided to.
The vapor deposition source 46 heated by the crucible 52, for example, metal aluminum or aluminum oxide is evaporated on the base film 1 or the like guided on the cooled coating drum, and if necessary, oxygen is added. For example, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed on the base film through the mask 48 while oxygen gas or the like is ejected from the gas outlet 47 and supplied.

Next, for example, a base film 1 or the like on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is wound around a take-up roll 51 through guide rolls 49 and 50 to have a inorganic oxide vapor deposition film. The material film 1 etc. can be manufactured.
The degree of vacuum of the take-up chamber is 10 ⁰ to 10 ⁻⁵ mbar, preferably 10 ⁻¹ to 10 ⁻⁴ mbar. Further, the degree of vacuum of the vapor deposition chamber is preferably 10 ⁻² to 10 ⁻⁸ mbar, preferably 10 ⁻³ to 10 ⁻⁷ mbar before introducing the oxygen gas, and is preferably 10 ⁻³ to 10 ⁻⁷ mbar after introducing the oxygen gas. ^-1 to 10 ^-6 mbar, preferably 10 ^-2 to 10 ^-5 mbar. Moreover, as conveyance speeds, such as a base film, 10-800 m / min, Preferably 50-600 m / min is desirable.
The above exemplification is an example, and the present invention is not limited thereby.

In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or the above-described winding type vacuum vapor deposition apparatus is used to connect the two in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form an inorganic oxide vapor-deposited film composed of two or more multilayer films.
After forming a vapor-deposited film of an inorganic oxide on a substrate by chemical vapor deposition or physical vapor deposition as described above, the vapor-deposited film may be further subjected to glow discharge treatment, plasma treatment, or microwave treatment. Good. This further improves the adhesion between the deposited film and the following gas barrier coating film.

3. Gas barrier coating film It is preferable to provide a gas barrier coating film on the barrier thin film layer in order to further improve the gas barrier property of the oxygen moisture absorbing pouch of the present invention. The gas barrier coating film will be described. The gas barrier coating film contains an alkoxide and a water-soluble polymer. Specifically, as the gas barrier coating film, a general formula: R ¹ _n M (OR ² A gas barrier coating film made of a gas barrier composition obtained by polycondensation of a composition containing at least one alkoxide represented by _m , polyvinyl alcohol and / or ethylene / vinyl alcohol by a sol-gel method is used.

The alkoxide that can be suitably used in the present invention has a general formula: R ¹ _n M (OR ² ) _m (wherein M is a metal atom, R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and 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 kind of a partial hydrolyzate of alkoxide or a hydrolyzed condensate of alkoxide can be used. . In addition, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which one or more was hydrolyzed, and its mixture may be sufficient. Further, the hydrolysis condensate represents a dimer or more of a partially hydrolyzed alkoxide, and a 2-6 mer is usually used.

As the metal atom represented by M in the above 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 as a mixture of two or more different metal atom alkoxides in the same solution.
Specific examples of the organic group R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n- Examples thereof include alkyl groups such as 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. 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, or the like is 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.

Further, alkylalkoxysilane R ^b _m Si (OR ^c ) _4-m can be used (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.
Among the alkoxides, specific examples of zirconium alkoxides in which M is Zr include tetramethoxyzirconium Zr (O—CH ₃ ) ₄ , tetraethoxyzirconium Zr (O—C ₂ H ₅ ) ₄ , tetraipropoxyzirconium Zr. _{(O-Iso-C 3 H} 7) 4, tetra-n-butoxy zirconium _{Zr (O-C 4 H 9} ) 4 and the like can be preferably used.
Among the above alkoxides, specific examples of titanium alkoxides in which M is Ti include tetramethoxytitanium Ti (O—CH ₃ ) ₄ , tetraethoxytitanium Ti (O—C ₂ H ₅ ) ₄ , and tetraisopropoxytitanium Ti. _{(O-Iso-C 3 H} 7) 4, tetra-n-butoxy titanium _{Ti (O-C 4 H 9} ) 4 and the like can be preferably used.
Among the alkoxides, specific examples of aluminum alkoxides in which M is Al include tetramethoxyaluminum Al (O—CH ₃ ) ₄ , tetraethoxyaluminum Al (O—C ₂ H ₅ ) ₄ tetraisopropoxyaluminum Al ( _{O-Iso-C 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (O-C 4 H 9} ) 4 and the like can be preferably used.

  Two or more kinds of these alkoxides may be mixed and used. In particular, by using a mixture of alkoxysilane and zirconium alkoxide, the toughness, heat resistance and the like of the resulting laminated film are improved, and a decrease in the retort resistance of the film during stretching can be avoided. The amount of zirconium alkoxide used is in the range of 10 parts by weight or less, preferably about 5 parts by weight, based on 100 parts by weight of alkoxysilane. When the amount exceeds 10 parts by weight, the formed composite polymer is easily gelled, the brittleness of the composite polymer is increased, and the composite polymer layer is easily peeled off when a base film or the like is coated.

  In particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting film is lowered, and the heat resistance of the substrate film and the like is remarkably improved. The amount of titanium alkoxide used is in the range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of alkoxysilane. When the amount exceeds 5 parts by weight, brittleness of the formed composite polymer increases, and the composite polymer is easily peeled off when a base film or the like is coated.

  In the present invention, a silane coupling agent is preferably used in combination with the alkoxide. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is suitable. Examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Two or more kinds of such silane coupling agents may be mixed and used. The amount of the silane coupling agent used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. When 20 parts by weight or more is used, the composite polymer formed is increased in rigidity and brittleness, and the insulation and workability of the composite polymer layer are lowered.

In the present invention, the composition (coating liquid) for forming a gas barrier coating film contains polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer as a water-soluble polymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance, and the like of the obtained coating film are remarkably improved. Furthermore, a laminated film in which polyvinyl alcohol and ethylene / vinyl alcohol copolymer are combined is excellent in hot water resistance and gas barrier property after hot water treatment in addition to 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 600 parts by weight, preferably about 50 to 400 parts by weight, with respect to 100 parts by weight of the total amount of the alkoxide. If it exceeds 600 parts by weight, the brittleness of the composite polymer increases, and the water resistance and weather resistance of the resulting laminated film also deteriorate. When the amount is less than 5 parts by weight, the gas barrier property is lowered.

  In the present invention, the above composition (coating solution) is applied onto the barrier thin film layer, and the composition is polycondensed by a sol-gel method to obtain a coating film. As the sol-gel catalyst, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and NN-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.

  In the present invention, the above composition may contain an acid instead of the tertiary amine or further. The acid is used as a catalyst for a sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent.

  In the present invention, the composition for forming a gas barrier coating film contains water 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 alkoxide. It is preferable. 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 cross-linked to form a porous polymer having a low density. . Porous polymers cannot improve the gas barrier properties of moisture-absorbing laminates and the like. When the amount of water is less than 0.8 mol, the hydrolysis reaction hardly proceeds.

Moreover, it is preferable that the composition for gas-barrier coating film formation contains an organic solvent. As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like are used.
The polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a composition (coating liquid) containing the alkoxide, silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. Is done. When employing a combination of polyvinyl alcohol and ethylene-vinyl alcohol copolymer, it is preferable to use n-butanol. An ethylene-vinyl alcohol copolymer solubilized in a solvent is commercially available, for example, as Soarnol (trade name). The amount of the organic solvent used is usually 30 to 500 parts by weight per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer, acid, and sol-gel method catalyst. .

A method for forming the gas barrier coating film will be described below.
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, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier coating solution. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.
Next, the gas barrier coating solution is applied by a conventional method on the barrier thin film layer provided on one surface of the base film or the like, and dried. By the drying, the polycondensation of the alkoxide, metal alkoxide, silane coupling agent, and vinyl alcohol polymer further proceeds to form a composite polymer layer. Preferably, the above operation is repeated to laminate a plurality of composite polymer layers.
Finally, the film coated with the coating solution is subjected to a temperature of 50 ° C. to 300 ° C., preferably 70 ° C. to 200 ° C. under a normal environment, for 0.005 minutes to 60 minutes, preferably 0.01 minutes. By heating and drying for 10 minutes, condensation is performed and a gas barrier coating film can be formed.

In the present invention, an ethylene / vinyl alcohol copolymer or a composition using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol may be used instead of the vinyl alcohol polymer. A laminated film using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol is further improved in gas barrier properties after hot water treatment such as boil treatment and retort treatment.
As another aspect of forming the gas barrier coating film, the following laminated film is preferably formed in order to improve the gas barrier property after the hot water treatment.

That is, a composition containing polyvinyl alcohol is previously formed on at least one surface of a substrate film or the like to form a first composite polymer layer, and then the ethylene / vinyl alcohol copolymer is contained on the coated surface. The composition is applied to further form a second composite polymer layer. Thereby, the gas barrier property of the laminated film obtained improves.
Furthermore, in the present invention, a plurality of gas barrier coating films may be formed on the barrier thin film layer. By providing a plurality of gas barrier coating films, the gas barrier property can be further improved.

Examples of the method for applying the gas barrier coating film forming composition include one or more times by a coating means such as a roll coat such as a gravure coater, a spray coat, a spin coat, a dipping, a brush, a barcode, and an applicator. With this coating, it is possible to form the gas barrier coating film of the present invention having a dry-baked film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance.
In the embodiment of the present invention, after providing the vapor deposition layer and the gas barrier coating film on the base film, etc., the vapor deposition layer is further provided, and the gas barrier coating film is formed on the vapor deposition layer in the same manner as described above. May be. Thus, by increasing the number of laminated layers, it is possible to realize a laminated film having further excellent gas barrier properties.

4). Moisture-absorbing resin film Next, the moisture-absorbing resin film constituting the moisture-absorbing laminate in the oxygen moisture-absorbing pouch of the present invention will be described.
Such a moisture-absorbing resin film is present or inherent in a packaged product such as moisture present in a head space or the like in a packaged product filled and packaged with contents, or moisture generated due to changes in storage conditions such as temperature changes. A resin composition that absorbs and captures moisture and optionally contains a desiccant, a synthetic resin, and other additives, and that is formed into a film can be used.

  And, since the oxygen moisture-absorbing pouch of the present invention is mainly used for packaging of precision equipment such as electronic components, electronic devices, electronic equipment, printed boards, etc., in order to prevent deterioration of its performance, As the desiccant used for the moisture-absorbing resin film, it is desirable to use a desiccant that has a high moisture absorption rate, has an excellent moisture absorption capability even under low humidity, and does not have corrosivity or deliquescence. . Examples of such a desiccant include zeolite, molecular sieve, silica gel, and activated alumina. These may be used alone or in admixture of two or more. Furthermore, as said desiccant, it is preferable to use a thing with an average particle diameter of 1 micrometer-20 micrometers so that the function of a desiccant can be exhibited to the maximum, and as content in the resin composition of the said desiccant, Although it varies depending on the kind of the desiccant, it is generally 10 to 40% by weight, preferably 20 to 35% by weight. When the content of the desiccant in the resin composition is 10% by weight, or even less than 20% by weight, the desired moisture absorption effect cannot be obtained, and when the content exceeds 40% by weight, or even 35% by weight, The rigidity of the resulting moisture-absorbing resin film is reduced.

  Moreover, as a synthetic resin used for the above-mentioned moisture-absorbing resin film, even if a desiccant is added, it maintains the flow characteristics to such an extent that it can be easily processed into a film, and it absorbs moisture. Since the innermost layer of the laminate may be formed, it is desirable to have heat sealing performance.

  As a synthetic resin having such properties, a thermoplastic resin, specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polymerized using a metallocene catalyst. Ethylene-α / olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid Polyolefin resins such as acid methyl copolymer, ethylene-propylene copolymer, methyl pentene polymer, polybutene polymer, polyethylene or polypropylene are not suitable for acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Acid modification modified with saturated carboxylic acid Polyolefin resins, polyvinyl acetate resins, poly (meth) acrylic resin, a resin such as polyvinyl chloride resin can be used.

  Furthermore, the thermoplastic resin is 1 g / 10 min to 6 g / 10 min under the conditions specified in JIS K7210 from the viewpoints of processability to film when adding a desiccant, tensile strength, and stress cracking resistance. Preferably, it has a melt flow rate of 2 g / 10 min to 4 g / 10 min. When the melt flow rate is 1 g / 10 minutes, or even less than 2 g / 10 minutes, the workability of the film when a desiccant is added deteriorates, and the melt flow rate is 6 g / 10 minutes. Further, if it exceeds 4 g / 10 minutes, cracking occurs due to an external load such as bending or stretching during the manufacture of the packaging bag, and the desired heat sealing performance or moisture absorption ability cannot be obtained.

  In addition, the moisture-absorbing resin film includes, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, and antifungal properties. Various plastic compounding agents and additives can be added for the purpose of improving and modifying electrical characteristics, strength, etc. Depending on the case, it can be added arbitrarily.

  In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Etc. can be arbitrarily used, and further, a modifying resin or the like can also be used.

  In the present invention, a resin composition in which the desiccant, the thermoplastic resin, and an additive as necessary are mixed is used. By using this, an extrusion such as a T-die extrusion method or an inflation molding method is used. A water-absorbing resin film is produced by forming a film by molding, calendar molding, solution casting molding, or the like. The film thickness of the moisture-absorbing resin film is 5 μm to 300 μm, preferably 9 to 100 μm.

  Further, as the above water-absorbing resin film, a resin composition containing the above desiccant and thermoplastic resin, and a resin composition containing the above thermoplastic resin as a main component of a vehicle are prepared, and these are coextruded. A moisture-absorbing coextruded multilayer laminated film including a moisture-absorbing resin layer and a heat-sealable resin layer that are laminated to form a film can also be used. The thermoplastic resin constituting the moisture-absorbing resin layer also has a melt flow rate of 1 g / 10 min to 6 g / 10 min, preferably 2 g / 10 min to 4 g / 10 min, for the same reason as above. It is desirable to use Further, the content of the desiccant in the resin composition is generally 10% to 40% by weight, preferably 20% to 35% by weight for the same reason as described above.

  When describing a method for producing a moisture-absorbing coextruded multilayer laminated film including a moisture-absorbing resin layer and a heat-sealable resin layer constituting the moisture-absorbing resin film, first, a desiccant and a thermoplastic resin are mixed, Furthermore, one or two or more of the above-mentioned additives are optionally added as necessary, and if necessary, a solvent, a diluent, etc. are added and kneaded sufficiently to form a water-absorbing resin layer. A resin composition is prepared. On the other hand, one or more of the above-mentioned additives are optionally added to one or more of the above-described thermoplastic resins, and if necessary, a solvent, a diluent, etc. are added. And kneaded sufficiently to prepare a resin composition that forms a heat-sealable resin layer. Next, using these resin compositions, combining them, for example, co-extrusion molding using a T-die co-extruder, an inflation co-extruder, etc., the moisture-absorbing resin layer and the heat-sealable resin Water-absorbing co-extruded multilayer laminated films having various layer configurations composed of layers laminated in sequence can be produced.

As a moisture-absorbing coextrusion multilayer laminated film that can be produced in this way, the first layer is a layer that is coextrusion laminated in the order of a moisture-absorbing resin layer and the second layer is a heat-sealable resin layer. A moisture-absorbing coextruded multilayer laminated film composed of two types and two layers, a first layer as a heat-sealable resin layer, a second layer as a moisture-absorbing resin layer, and a third layer as a heat-sealable resin layer The coextruded multilayer laminated film which consists of 2 types of 3 layers of this invention which consists of the structure which carried out 3 layer coextrusion lamination in this order can be mentioned.
The above exemplification shows two examples of the moisture-absorbing coextruded multilayer laminated film constituting the moisture-absorbing resin film and the production method thereof, and the present invention is not limited to this.
The film thickness of the moisture-absorbing coextruded multilayer laminated film is 20 μm to 250 μm, preferably 30 μm to 190 μm in total thickness. And in said moisture coextrusion multilayer laminated film, as a film thickness of a moisture absorptive resin layer, it is desirable that it is a film thickness of 5 micrometers-50 micrometers, Preferably it is 20 micrometers-40 micrometers, As a film thickness of a heat sealable resin layer The film thickness is 1 μm to 100 μm, preferably 5 μm to 80 μm.

  If the film thickness of the moisture-absorbing coextruded multilayer laminated film is 20 μm, or even less than 30 μm, it is difficult to form the film itself, and the strength is reduced, and defects such as blurring and scratches are likely to occur. On the other hand, if it exceeds 250 μm, and more than 190 μm, it is not preferable from the viewpoints of the environment and cost. In addition, if the film thickness of the water-absorbing resin layer is 5 μm, and further less than 10 μm, the required water-absorbing physical properties cannot be sufficiently exhibited, and if it exceeds 50 μm and further 40 μm, the cost is increased. It is not preferable because it rises. Furthermore, if the thickness of the heat-sealable resin layer is 1 μm, and further less than 5 μm, the function as the seal layer is reduced, and if it exceeds 100 μm and further 80 μm, there is no problem with the sealing strength, but the cost Is not preferable from the environmental aspect.

5). Next, the oxygen-absorbing resin film constituting the oxygen-absorbing laminate in the oxygen-moisture-absorbing pouch of the present invention will be described.
As such an oxygen-absorbing resin film, oxygen present in a head space or the like in a packaged product filled and packaged with the content, oxygen contained in the content, or oxygen generated from the content, etc. Since it absorbs and traps oxygen present or contained in the packaged product, it contains an oxidizing resin and a transition metal catalyst, and if necessary, a thermoplastic resin as a binder, or A resin composition that optionally contains an additive such as a radical generator or a photosensitizer can be prepared and used as a film.

  In the present invention, the oxidizing resin has an unsaturated double bond unit in the main chain, skeleton, side chain, etc., and the unsaturated double bond portion is, for example, a chain reaction by radicals, etc. In addition, a material that exhibits an oxygen absorption function by being saturated by interaction with oxygen is used. Specifically, as the oxidizing resin constituting the oxygen-absorbing resin film, for example, the following materials can be used.

(1) Ethylenically unsaturated hydrocarbon polymer:
Ethylenically unsaturated hydrocarbon polymers include atactic-1,2-polybutadiene, EPDM rubber, polyoctenamer, 1,4-polybutadiene, syndiotactic-1,2-polybutadiene, partially polymerized unsaturated fatty acids and esters, Block or graft copolymers, hydrosite-like materials can be used. The molecular weight is preferably 1,000 or more.
Furthermore, an oxygen-absorbing anion or a thermoplastic resin can be added to the above-mentioned ethylenically unsaturated hydrocarbon polymer. As the oxygen-absorbing anion, ascorbate anion, thiolate anion, phenolate anion, or a mixture thereof, Examples of the thermoplastic resin include polyethylene, polyolefin, ethylene / vinyl acetate copolymer, butyl rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / And thermoplastic resins selected from the group consisting of styrene block copolymers, vinyl chloride homopolymers, vinyl chloride polymers and blends thereof.

で表わされる繰り返し単位を有する主鎖エチレン系不飽和炭化水素ポリマーであって、分子量が１,０００〜５００,０００の範囲であり、炭素−炭素の二重結合が、０.０００１ｅｑ／ｇ以上の割合で含有される熱可塑性樹脂を使用することができる。
式中、Ｒ₁は、水素原子、炭素原子数１〜１０のアルキル基、アリール基、アルキルアリール基、またはアルコキシ基であり、Ｒ₂およびＲ₃が各々水素原子、炭素原子数１〜１０のアルキル基、置換アリール基、非置換アリール基、−ＣＯＯＲ₄、−ＯＣＯＲ₅、シアノ基、またはハロゲン原子であり、Ｒ₄およびＲ₅は各々独立して炭素原子数１〜１０のアルキル基、アリール基、アルキルアリール基またはアルコキシ基であり、ｎは数平均分子量が１,０００〜５００,０００となるような整数である。
好ましくは、−Ｒ₁、Ｒ₂、Ｒ₃が、各々独立してメチル基、または水素原子である樹脂組成物が望ましい。 (2) Main chain ethylenically unsaturated hydrocarbon polymer:
The following chemical structural formula

A main chain ethylenically unsaturated hydrocarbon polymer having a repeating unit represented by: a molecular weight in the range of 1,000 to 500,000, and a carbon-carbon double bond of 0.0001 eq / g or more. A thermoplastic resin contained in a proportion can be used.
In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and having 1 to 10 carbon atoms. An alkyl group, a substituted aryl group, an unsubstituted aryl group, —COOR ₄ , —OCOR ₅ , a cyano group, or a halogen atom, and R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl A group, an alkylaryl group or an alkoxy group, and n is an integer having a number average molecular weight of 1,000 to 500,000.
Preferably, a resin composition in which —R ₁ , R ₂ and R ₃ are each independently a methyl group or a hydrogen atom is desirable.

(3) Polyether unit polymer:
The polyether unit polymer referred to in the present invention means a polymer containing an aromatic polyether unit, a polyalkylene ether unit (aliphatic polyether unit) or other generally known polyether unit as the polyether unit. These may be a single polymer or a copolymer.

  Examples of the polymer containing the aromatic polyether unit include polyphenylene ethers such as poly (2,6-dimethyl-1,4-phenylene ether) and poly (2,6-diethyl-1,4-phenylene ether), Or the copolymer containing these is mentioned. Examples of the polymer containing a polyalkylene ether unit include polymethylene glycol, polyethylene glycol, poly (1,2-propylene glycol), poly (1,3-propylene glycol), polytetramethylene glycol, poly (1,1, 2-butylene glycol), polyhexamethylene glycol and other linear and branched aliphatic ethers, as well as alicyclic ether monopolymers or copolymers such as cyclohexanediol condensates and cyclohexanedimethanol condensates A polymer is mentioned and what is random-copolymerized within an ether unit is also contained. Among the polymers, a polymer containing a polyalkylene ether unit is preferable, and in particular, a multi-block copolymer having a polyalkylene ether unit, that is, a polyester ether block copolymer (polyester) using an aromatic polyester and a polyalkylene ether. Thermoplastic elastomers), multi-block copolymers using aliphatic polyesters and polyalkylene ethers, hard segments composed of polymers of short-chain glycols and diisocyanates, and soft segments composed of polymers of diisocyanates and polyalkylene ethers Polyurethane-based thermoplastic elastomer having polyamide, polyamide polyether copolymer using polyamide and polyalkylene ether (block copolyether amide, block copolyether ester amide, It is desirable to use a lock copolyetherester ether amides).

  The polyalkylene ether units contained in these copolymers include polyalkylene ethers having a number average molecular weight of 400 to 6,000, preferably 600 to 4,000, particularly 1,000 to 3,000 (for example, Polyethylene glycol, poly (1,2- and 1,3-propylene glycol), polytetramethylene glycol, polyhexamethylene glycol and the like can be preferably used, and polytetramethylene glycol is particularly preferable. When the number average molecular weight of the polyalkylene ether unit is less than 400, sufficient oxygen absorption performance cannot be exhibited. On the other hand, those exceeding 6,000 are likely to cause phase separation in the system and are obtained by copolymerization or the like. The physical properties of the polymer are lowered, which is not preferable (see JP-A-2003-64250).

(4) Copolymers of ethylene and cyclopentene, cyclobutene, cycloptene, cyclooctene, cyclononene, or cyclohexene:
Specific examples of the copolymer include an ethylene-cyclopentene copolymer and an ethylene-4-vinylcyclohexene terpolymer (see JP-A-2003-504042).

(5) Polyamide resin:
As the polyamide resin, poly-m-xylylene-adipamide, nylon 6-6 can be used, and poly-m-xylylene adipamide, poly-m-xylylene sebacamide, and poly-m-xylylene can be used. Use homopolymers such as lensperamide, copolymers such as m-xylylene / p-xylylene adipamide copolymer, m-xylylene / p-xylylene piperamide copolymer, m-xylylene / p-xylylene azelamide copolymer can do.

Examples of aliphatic diamines forming the above polyamide resin include hexamethylene diamine, examples of cyclic diamines, piperazine, examples of aromatic diamines, p-bis (2-aminoethyl) benzene, examples of aromatic dicarboxylic acids As terephthalic acid.
Other constituent components of the above polyamide resin include benzylamine, 3-methylbenzylamine, metaxylylenediamine, paraxylylenediamine, N, N′-dimethylmetaxylylenediamine, N, N, N ′, N ′. -Tetramethylmetaxylylenediamine, N, N'-dimethylparaxylylenediamine, N, N, N ', N'-tetramethylparameter xylylenediamine, N, N'-diethylmetaxylylenediamine, N, N , N ′, N′-tetraethylmetaxylylenediamine, N, N′-diethylparaxylylenediamine, N, N, N ′, N′-tetraethylparaxylylenediamine, 1,3,5-tris (aminomethyl) ) Benzene, metaxylylenediamine or paraxylylenediamine and organic carboxylic acids such as stearic acid, oleic acid, lauric acid, tall oil fatty acid By reacting monocarboxylic acid and adipic acid, sebacic acid, dicarboxylic acid and other dicarboxylic acid and amide, metaxylylenediamine or paraxylylenediamine widely used as epoxy resin curing agent with formaldehyde and phenol Mannich base, adduct of metaxylylenediamine or paraxylylenediamine and vinyl compounds such as acrylonitrile, methyl methacrylate, etc., metaxylylenediamine or paraxylylenediamine and epoxy compounds such as bisphenol A epoxy resin, bisphenol F Adducts with epoxy resins, butyl glycidyl ether, etc., cured epoxy resins cured with these curing agents, and amino acids represented by tetraglycidyl metaxylylene diamine. Examples include group-containing epoxy compounds, isocyanate compounds typified by metaxylylene diisocyanate and paraxylylene diisocyanate, and polyurethanes derived from each, and even if a plurality of these compounds are blended to form a polyamide resin Good.

(6) Acid-modified polybutadiene:
Examples of the acid-modified polybutadiene include polybutadiene, polyisoprene, styrene-butadiene block copolymer, and acrylate or polyterpene produced by transesterification of poly (ethylene-methyl acrylate) (see JP-T-2002-505575). ).

(7) Hydroxyaldehyde polymer:
Hydroxy aldehydes such as glycol aldehyde and glyceraldehyde, aliphatic unsaturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde, aliphatic unsaturated aldehydes such as acrylic aldehyde, and fumaraldehyde, glycol aldehyde, glyceraldehyde Such as hydroxy aldehydes, alkoxy aldehydes such as 2-methoxyethanal, oxo aldehydes such as 2-oxopropanal, amino aldehydes such as 2-aminoethanal, halogen-substituted aldehydes such as 2-chloroethanal, cyclohexanecarbaldehyde, etc. Polymer obtained by polymerizing one or more of alicyclic aldehydes, aldehydes substituted with aromatic rings such as 2-phenylethanal, etc. It can be used.

  In the present invention, as the above-mentioned oxidizing resin, ethylene / methyl acrylate / cyclohexenyl methyl acrylate terpolymer, cyclohexenyl methyl acrylate / ethylene copolymer, cyclohexenyl methyl acrylate / styrene copolymer, cyclohexenyl methyl acrylate homopolymer or methyl acrylate / It is preferable to use a cyclohexenyl methyl acrylate copolymer or the like.

  The transition metal catalyst composing the oxygen-absorbing resin film mainly promotes radical decomposition reaction by applying energy such as ultraviolet light (UV), and starts oxygen absorption of the oxidizing resin shown above. It has a function such as expression, and is from a metal belonging to Group III to Group XI of the periodic table, for example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or a mixture thereof A selected transition metal can be used.

  As the transition metal, it is preferable to use a composition comprising Co, Cu, Fe, or other metals belonging to Group VIII of the periodic table, or a mixture thereof. It can also be used in the form of low-valent inorganic acid salts, organic acid salts or complex salts of the above transition metals. Examples of inorganic acid salts include halides such as chlorides, sulfur oxyacid salts such as sulfates, and nitrates. Nitrogen oxyacid salts, phosphorous oxyacid salts such as phosphates, silicates, and the like, and organic acid salts include carboxylates, sulfonates, phosphonates, and the like. Among these, carboxylates are most preferable, and specific examples thereof include acetic acid, propionate, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2 -Ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, lindelic acid, tuzu Examples thereof include transition metal salts such as acid, petroceric acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, sulfamic acid, and naphthenic acid.

  In the present invention, as the above transition metal catalyst, specifically, cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt oleate and cobalt stearate are preferably used.

  Furthermore, a thermoplastic resin may be added as a binder to the oxygen-absorbing resin film, and the same thermoplastic resin as that used for the moisture-absorbing resin layer is used as the thermoplastic resin. be able to. The above thermoplastic resin mainly has a certain degree of affinity for the oxidizing resin, is thermoplastic, and exhibits functions such as heat sealability.

  Further, in order to amplify the oxidation reaction of the oxidizing resin, a radical generator or a photosensitizer may be further added to the oxygen-absorbing resin film, for example, benzoin, acenaphthenequinone, benzoin methyl ether. Benzoin such as benzoin ethyl ether and benzoin isopropyl ether, and alkyl ethers thereof; acetophenone, methyl ethyl ketone, valerophenone, hexaphenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 , 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, etc. Tophenones; anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal Generally known photoinitiators such as ketals such as benzyldimethyl ketal; benzophenones such as benzophenone or xanthones are used.

  These photo-radical initiators can be used in combination with one or more known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine type. In addition, at least one selected from ketocarbonyl compounds, amine compounds, transition metals and their compounds, and halogen compounds can be used.

Examples of the ketocarbonyl compound include α-diketone, α-ketoaldehyde, α-ketocarboxylic acid, α-ketocarboxylic acid ester, specifically diacetyl, 2,3-pentanedione, 2,3-hexanedione, benzyl, Α-diketones such as 4,4-dimethoxybenzyl, 4,4-oxybenzyl, 4,4-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, 1,2-cyclohexanedione, Α-Ketoaldehydes such as methyl glyoxal and phenylglyoxal, pyruvate, benzoylformate, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate and butyl phenylpyruvate can be used.
Acetyltetralone, Linderic acid, Margaric acid, Stearic acid, Adipic acid, Diacetylbenzoin, Distearoylmethane, methane, and dibivaloylmethane can also be used.

In the present invention, as the above radical generator or photosensitizer, specifically, benzophenone, benzoin methyl ether, or the like is preferably used.
In the resin composition including the oxidizing resin and the transition metal catalyst constituting the oxygen-absorbing resin film, the mixing ratio of the oxidizing resin and the transition metal catalyst is as follows: transition metal catalyst with respect to 100 parts by weight of the oxidizing resin However, it is preferable to prepare the resin composition at 0.001 to 10 parts by weight. If the transition metal catalyst is less than 0.001, the catalytic action is low and the oxidation reaction does not proceed. If the transition metal catalyst exceeds 10 parts by weight, the amount of the catalyst is too large and other side reactions occur. It is not preferable because the cost increases. In the present invention, when a radical generator or a photosensitizer is added, it is preferably added at a blending ratio of 0.001 to 10 parts by weight with respect to 100 parts by weight of the oxidizing resin. Furthermore, when adding a thermoplastic resin, it is also preferable to add in the mixing | blending ratio of 50-100 weight part similarly with respect to 100 weight part of oxidizing resins.

  In the present invention, the resin composition containing the oxidizing resin prepared above and a transition metal catalyst is used. For example, a molding method such as a T-die extrusion molding method, an inflation molding method, a calendar molding method, or a casting molding method. To form an oxygen-absorbing resin film. The film thickness of the oxygen-absorbing resin film is 5 to 300 μm, preferably 9 to 100 μm.

  Further, as the above oxygen-absorbing resin film, a resin composition containing the above-mentioned oxidizing resin and a transition metal catalyst is prepared, and a resin composition containing the above-mentioned thermoplastic resin as a main component of a vehicle is also prepared. The two resin compositions can be used to form a film by co-extrusion lamination, and an oxygen-absorbing co-extrusion multilayer laminated film including the oxygen-absorbing resin layer and the heat-sealable resin layer can also be used. .

  The production method of the oxygen-absorbing coextruded multilayer laminated film including the oxygen-absorbing resin layer and the heat-sealable resin layer constituting the oxygen-absorbing resin film will be described. First, an oxidizing resin and a transition metal catalyst are mixed. If necessary, a thermoplastic resin as the above-mentioned binder, or a radical generator, a photosensitizer, or one or more other additives are optionally added, and if necessary, a solvent. Then, a diluent or the like is added and sufficiently kneaded to prepare a resin composition that forms an oxygen-absorbing resin layer. On the other hand, one or more of the above-mentioned additives are optionally added to one or more of the above-described thermoplastic resins, and if necessary, a solvent, a diluent, etc. are added. And kneaded sufficiently to prepare a resin composition that forms a heat-sealable resin layer. Next, using these resin compositions, combining them, for example, co-extrusion molding using a T-die co-extruder, an inflation co-extruder, etc., the oxygen-absorbing resin layer and the heat-sealable resin Oxygen-absorbing coextruded multilayer laminated films having various layer configurations composed of layers laminated in sequence can be produced.

As an oxygen-absorbing coextruded multilayer laminated film that can be produced in this way, the first layer is formed by coextrusion lamination of two layers in the order of the oxygen-absorbing resin layer and the second layer in the order of the heat-sealable resin layer. An oxygen-absorbing coextruded multilayer laminated film composed of two types and two layers, a first layer as a heat-sealable resin layer, a second layer as an oxygen-absorbing resin layer, and a third layer as a heat-sealable resin layer The coextruded multilayer laminated film which consists of 2 types of 3 layers of this invention which consists of the structure which carried out 3 layer coextrusion lamination in this order can be mentioned.
The above exemplification shows two examples of the oxygen-absorbing coextruded multilayer laminated film constituting the oxygen-absorbing resin film and the production method thereof, and the present invention is not limited to this.
The film thickness of the oxygen-absorbing coextruded multilayer laminated film is 20 μm to 250 μm in total thickness, preferably 30 μm to 190 μm. And in said oxygen coextrusion multilayer laminated film, as a film thickness of an oxygen absorptive resin layer, it is desirable that it is a film thickness of 5 micrometers-50 micrometers, Preferably it is 10 micrometers-30 micrometers, As a film thickness of a heat sealable resin layer The film thickness is 5 μm to 100 μm, preferably 10 μm to 80 μm.

  When the film thickness of the oxygen-absorbing coextruded multilayer laminated film is 20 μm, or even less than 30 μm, it is difficult to form the film itself, and the strength is reduced, and defects such as blurring and scratches are likely to occur. On the other hand, if it exceeds 250 μm, and more than 190 μm, it is not preferable from the viewpoints of the environment and cost. In addition, if the film thickness of the oxygen-absorbing resin layer is 5 μm, more preferably less than 10 μm, the required water absorption physical properties cannot be sufficiently exhibited, and if it exceeds 50 μm, more than 30 μm, the cost is increased. It is not preferable because it rises. Furthermore, when the film thickness of the heat-sealable resin layer is 5 μm, and further less than 10 μm, the function as the seal layer is lowered, and when it exceeds 100 μm and further 80 μm, there is no problem in sealing strength, but the cost Is not preferable from the environmental aspect.

6). Oxygen moisture-absorbing resin film In the oxygen moisture-absorbing pouch and the like of the present invention, an oxygen-moisture-absorbing film can be used in place of the moisture-absorbing laminate or the oxygen-absorbing laminate. As such an oxygen moisture-absorbing film, a two-layer structure of a moisture-absorbing resin layer containing the above desiccant and a thermoplastic resin, and an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, etc. And a multilayer laminated film having a three-layer structure of a heat-sealable resin layer, a moisture-absorbing resin layer, and an oxygen-absorbing resin layer.

  The production method of the oxygen moisture absorbing film will be described. First, a desiccant and a thermoplastic resin are mixed, and optionally one or more of the above additives are added, and further required. If so, add a solvent, diluent, etc., knead well, prepare a resin composition to form a moisture-absorbing resin layer, further mix the oxidizing resin and the transition metal catalyst, further if necessary One or two or more of a thermoplastic resin as a binder, a radical generator or a photosensitizer, and other additives are optionally added, and if necessary, a solvent, a diluent, etc. Add and knead well to prepare a resin composition that forms an oxygen-absorbing resin layer. On the other hand, one or more of the above thermoplastic resins are used as the main component of the vehicle, and if necessary, one or more of the above additives are optionally added, and if necessary, a solvent. Then, a diluent or the like is added and sufficiently kneaded to prepare a resin composition that forms a heat-sealable resin layer. Next, using these resin compositions, combining them, for example, co-extrusion molding using a T-die co-extruder, an inflation co-extruder, etc., the oxygen-absorbing resin layer and the heat-sealable resin Oxygen moisture-absorbing co-extruded multilayer laminated films having various layer configurations composed of layers laminated in sequence can be produced.

  As the oxygen moisture-absorbing coextruded multilayer laminated film that can be produced in this manner, the first layer was co-extrusion laminated in the order of the moisture-absorbing resin layer and the second layer was the oxygen-absorbing resin layer. Oxygen moisture-absorbing coextrusion multilayer laminated film consisting of 2 types and 2 layers comprising the structure, the first layer is a heat-sealable resin layer, the second layer is an oxygen-absorbing resin layer, and the third layer is moisture-absorbing An oxygen-moisture coextruded multi-layer laminate film comprising two types and three layers of the present invention having a constitution in which three layers are co-extrusion laminated in the order of the resin layer can be mentioned.

The above exemplifications illustrate one or two examples of the moisture-absorbing coextrusion multilayer laminated film constituting the oxygen moisture-absorbing resin film and the production method thereof, and the present invention is not limited thereto. .
The film thickness of the oxygen moisture-absorbing coextruded multilayer laminated film is 20 μm to 200 μm, preferably 30 μm to 150 μm in total thickness. In the moisture coextruded multilayer laminated film, the thickness of the moisture absorbing resin layer is desirably 5 μm to 50 μm, preferably 20 μm to 40 μm for the same reason as described above, and absorbs oxygen. The film thickness of the heat-resistant resin layer is 5 μm to 50 μm, preferably 10 μm to 30 μm. The film thickness of the heat-sealable resin layer is 5 μm to 100 μm, preferably 10 μm to 80 μm. It is desirable to be.

7). Heat-sealable resin film In the present invention, when the above-described moisture-absorbing resin film or oxygen-absorbing resin film does not have heat-sealing performance, the heat-sealable resin film is further formed on the moisture-absorbing resin film. Provide a film. The resin used to form the heat-sealable resin film may be any resin that can be melted by heat and fused to each other. Specifically, a thermoplastic resin used for the moisture-absorbing resin film is used. Can be used.

  Furthermore, the above heat-sealable resin film includes, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, and antifungal properties. Various plastic compounding agents and additives can be added for the purpose of improving and modifying electrical characteristics, strength, etc. Depending on the case, it can be added arbitrarily. In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Etc. can be arbitrarily used, and further, a modifying resin or the like can also be used.

  In the present invention, a thermoplastic resin and a resin composition mixed with additives as required are used, and this is used to perform extrusion molding such as T-die extrusion molding and inflation molding, and calendar molding. Then, it is formed into a film by solution casting molding or the like to produce a heat-sealable resin film. The film thickness of the heat-sealable resin film is 5 μm to 300 μm, preferably 9 to 100 μm.

8). Moisture-absorbing laminate, oxygen-absorbing laminate, and method for producing oxygen-moisture-absorbing laminate Next, the moisture-absorbing laminate, the oxygen-absorbing laminate, and the oxygen-moisture-absorbing structure constituting the oxygen-moisture-absorbing pouch of the present invention The manufacturing method of a laminated body is demonstrated.
First, the method for producing the moisture-absorbing laminate will be described. The moisture-absorbing laminate includes the above-described barrier thin film layer, or a base film provided with the barrier thin film layer and a barrier coating film, and a moisture-absorbing resin film. , And if necessary, heat lamination resin film is laminated via an adhesive layer for laminating, etc., or laminating while laminating various resins etc. via an anchor coating agent layer, etc. It can be manufactured using an extrusion laminate lamination method or the like.

Examples of the adhesive for laminating include, for example, polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, or polyacrylate ester adhesives composed of copolymers of these with methyl methacrylate, Cyanoacrylate adhesive, ethylene copolymer adhesive consisting of a copolymer of ethylene and vinyl acetate, cellulose adhesive, polyester adhesive, polyamide adhesive, alkali metal silicate, low melting point glass It is possible to use an adhesive such as an inorganic adhesive made of, for example. The adhesive can be applied by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or a printing method, and is 0.1 to 10.0 g / m ^{2 in} a dry state. It is desirable to coat so that

In addition, in the above, as the anchor coating agent constituting the anchor coating agent layer, for example, various aqueous or oil-based anchor coating agents such as organic titanium-based, isocyanate-based, polyethyleneimine-based, polyptadiene-based alkyl titanate, etc. are used. can do. The anchor coating agent can be coated using, for example, a coating method such as roll coating, gravure roll coating, kiss coating, and the coating amount is 0.1 to 5.0 g / m ^{2 in} a dry state. desirable.

  Examples of the melt-extruded resin layer in the melt-extrusion laminate method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, etc. One or more of these thermoplastic resins can be used. Further, in the melt extrusion laminate lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coat agent layer such as the above-described anchor coat agent.

In the present invention, when performing the above-described lamination, if necessary, for example, pretreatment such as corona discharge treatment, ozone treatment, flame treatment, and plasma treatment is performed on the surface of each substrate to be laminated. Can be applied arbitrarily.
In addition, for the oxygen-absorbing laminate and the oxygen-moisture-absorbing laminate, the oxygen-absorbing resin film or the oxygen-moisture-absorbing resin film is used instead of the water-absorbing resin film, respectively. Can be manufactured.

  In addition, since the oxygen moisture absorbing pouch of the present invention is usually subjected to severe physical and chemical conditions, the laminate constituting the oxygen moisture absorbing pouch is required to have strict packaging suitability, Various conditions such as anti-deformation strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, and hygiene are required. For this reason, in addition to the above materials, Other materials satisfying the above conditions can be arbitrarily used and laminated to produce a moisture-absorbing laminate or an oxygen-absorbing laminate.

Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate. Copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, Poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin Resin, Polycar Nate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose resin film or sheet can be selected arbitrarily Can be used.
Furthermore, in the present invention, a resin film or sheet having a barrier property that prevents permeation of synthetic paper, water vapor, water, and the like can be used according to other characteristics required for the oxygen-water-absorbing pouch. .

9. Oxygen-moisture-absorbing pouch of the present invention and method for producing a packaged product using the same Next, the method for producing the oxygen-moisture-absorbing pouch of the present invention will be described. For example, the moisture-absorbing pouch produced by the above-described method is described. A laminated body and an oxygen-absorbing laminated body are prepared, and the water-absorbing resin film and the oxygen-absorbing resin film of the inner layer are opposed to each other, and are folded or overlapped, for example, Heat seal forms such as side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, palm-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Thus, it is possible to produce oxygen moisture absorbing pouches having various forms by heat sealing.

Furthermore, in the present invention, two oxygen-water-absorbing laminates are prepared and folded with the oxygen-water-absorbing resin film faces opposite to each other, or the two sheets are overlapped, and the peripheral edge is heat sealed. Thus, the oxygen moisture-absorbing pouch having various forms can be manufactured by providing the seal portion.
In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
The oxygen-moisture-absorbing pouch of the present invention produced as described above is filled with various precision equipment such as electronic components, electronic devices, electronic equipment, printed boards, etc., and packaged products of various forms are obtained. It can be manufactured.
In the present invention, when filling and packaging the contents from the opening in the oxygen moisture absorbing pouch, before filling, after filling, or simultaneously with filling, on the inner surface of the packaging bag, The packaged product of the present invention is manufactured by irradiating ultraviolet light from the inner surface side, and then heat-sealing the opening of the packaging bag to form a sealed portion and sealing it.

  In the present invention, by irradiating the inner surface of the oxygen moisture absorbing pouch with ultraviolet light from the inner surface side as described above, the ultraviolet light reaches the oxygen absorbing resin layer or the film thereof very well, Then, ultraviolet light acts on the transition metal catalyst, which is activated, thereby causing, for example, a radical to attack an unsaturated bond such as a cyclohexene ring as an oxidizing resin, and bonding oxygen from a chain reaction, It has an oxygen collecting function of absorbing.

In the present invention, it is also possible to irradiate the laminate in the state of the original film before bag making with ultraviolet light, and then carry out bag making, filling and packaging of contents, and the like.
In the above, an ultraviolet (UV) irradiation device using a high-pressure mercury lamp (for example, model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.) or the like can be used as an ultraviolet irradiation device that irradiates ultraviolet light. As described above, the ultraviolet irradiation method can be applied to the inner surface of the packaging bag from the inner surface side, for example, before, after, or simultaneously with the contents. as, for example, as the intensity of ultraviolet rays, as the integrated quantity of ^{light, 500mJ / cm 2 ~2000mJ / cm} 2, preferably at ^{500mJ / cm 2 ~1000mJ / cm 2} , as the irradiation time of the ultraviolet rays, a lamp light intensity Irradiation can be performed in a time period satisfying the above integrated light quantity by the correlation, for example, 10 seconds to 80 seconds. In the above, if it is less than 500 mJ / cm ² , the ultraviolet light energy is insufficient and the oxidation reaction tends to be insufficient, and if it exceeds 2000 mJ / cm ² , the influence on the film is large, making it difficult to use as a film. It is not preferable because there is a fear of becoming.
Next, the present invention will be described more specifically with reference to examples.

[Example 1]
1. Manufacture of moisture-absorbing laminate (1) Manufacture of moisture-absorbing resin film First, the following resin compositions (a) to (c) were prepared.
(A) First layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight and synthetic silica 0.5 weight Part, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylene bisoleic acid amide were sufficiently kneaded to prepare a resin composition forming the first layer.

(B) Second layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight, and synthetic silica 0.5 weight Part and 30.0 parts by weight of silica gel having a particle size of 8 μm as a desiccant were sufficiently kneaded to prepare a resin composition for forming the second layer.

(C) Third layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight, and synthetic silica 0.5 weight And a resin composition for forming a third layer was prepared.

  Next, using the resin compositions (a) to (c) prepared above, and using an air-blowing co-extrusion film forming machine for blowing these, the first layer of the resin composition of (a) is 10 μm, A water-absorbing resin film consisting of three layers and having a total thickness of 50 μm is manufactured by co-extrusion so that the second layer of the resin composition of (b) is 30 μm and the third layer of the resin composition of (c) is 10 μm. did.

(2) Formation of a barrier thin film layer on a base film A biaxially stretched polyethylene terephthalate film is used as a base film, and the above biaxially stretched polyethylene terephthalate film is first mounted on a delivery roll of a plasma chemical vapor deposition apparatus. did. Next, this was fed out, and an organic silicon oxide vapor deposition film having a thickness of 200 mm was formed as a barrier thin film layer on the biaxially stretched polyethylene terephthalate film under the following vapor deposition conditions.
(Deposition conditions)
Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 2.5 (unit: slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film ^- forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power: 35kW

(3) Manufacture of moisture-absorbing laminate A two-component curable urethane-based adhesive is attached to the barrier thin film layer surface (organic silicon oxide deposition film surface) of the base film on which the barrier thin film layer manufactured in (2) above is formed. The agent was laminated by a gravure roll coating method so as to be 4.0 g / m ² in a dry state, and bonded to the moisture-absorbing resin film produced in the above (1) to produce a moisture-absorbing laminate.

2. Manufacture of oxygen-absorbing laminate (1) Manufacture of oxygen-absorbing resin film First, the following resin compositions (a) to (c) were prepared.
(A) First layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight and synthetic silica 0.5 weight Part, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylene bisoleic acid amide were sufficiently kneaded to prepare a resin composition forming the first layer.

(B) Second layer As the oxidizing resin, [ethylene / methyl acrylate / methylcyclohexene methyl acrylate copolymer] 100.0 parts by weight, and as the transition metal catalyst, [cobalt 2-ethylhexanoate] 0.01 parts by weight Then, 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] as a radical photopolymerization initiator was sufficiently kneaded to prepare a resin composition for forming the second layer.

(C) Third layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight, and synthetic silica 0.5 weight And a resin composition for forming a third layer was prepared.

  Next, using the resin compositions (a) to (c) prepared above, and using an air blown inflation co-extrusion film forming machine, the first layer of the resin composition (a) is 20 μm, A second layer made of the resin composition of (b) was co-extruded so as to be 10 μm and a third layer of the resin composition of (c) was made 20 μm to produce an oxygen-absorbing resin film having a total thickness of 50 μm consisting of three layers. .

(2) Production of oxygen-absorbing laminate The barrier thin film layer produced in “(2) Formation of barrier thin film layer on substrate film” in “1. Production of moisture-absorbing laminate” is formed. A two-component curable urethane-based adhesive is laminated on the surface of the barrier film of the base film (deposited film surface of organic silicon oxide) by a gravure roll coat method so as to be 4.0 g / m 2 in a dry state. The oxygen-absorbing laminate was manufactured by bonding to the oxygen-absorbing resin film.

3. Manufacture of oxygen moisture-absorbing pouches and packaging products Prepare the moisture-absorbing laminate and the oxygen-absorbing laminate manufactured above, so that the moisture-absorbing resin film surface and the oxygen-absorbing resin film surface face each other. The oxygen moisture-absorbing pouch of the present invention comprising a three-side sealed soft packaging bag having an opening on the upper side was formed by three-way heat-sealing the end portions around the outer periphery.
Furthermore, using an ultraviolet ray irradiation device [manufactured by Eye Graphics, model: ECS-401GX], an ultraviolet ray of 1000 mJ / cm ² is irradiated on the inner surface of the oxygen moisture absorbing pouch produced as described above, and a printed circuit board is placed. The opening part was heat-sealed to form an upper seal part to produce the packaged product of the present invention.

[Example 2]
According to the following steps, a plasma treatment surface was provided on the barrier thin film layer provided on the substrate, and a gas barrier coating film was formed on the plasma treatment surface. A moisture-absorbing resin film or oxygen was formed on the gas barrier coating film. Except that the absorbent resin film was laminated, the oxygen-moisture-absorbing pouch and packaged product of the present invention were produced in the same manner as in Example 1.
1. Formation of Plasma Treated Surface A glow discharge plasma generator is used on the barrier thin film layer surface (organic silicon oxide vapor deposition film surface) provided on the substrate, and the power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = Using a mixed gas of 7.0: 2.5 (unit: slm), oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 8.0 × 10 ⁻⁵ mbar and a processing speed of 100 m / min, and organic A plasma-treated surface was formed in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.

2. Lamination of gas barrier coating film According to the composition shown in the following (Table 1), a prepared composition a. A pre-prepared composition b. In a mixed solution comprising an aqueous polyvinyl alcohol solution, isopropyl alcohol and ion-exchanged water. A hydrolyzed solution consisting of ethyl silicate, silane coupling agent, isopropyl alcohol, 0.5N hydrochloric acid aqueous solution and ion-exchanged water was added and stirred sufficiently to obtain a colorless and transparent barrier coating solution.

  Next, the above 1. Using the gas barrier composition produced above on the plasma-treated surface of the organic silicon oxide vapor-deposited film formed by coating with the gravure roll coat method, and then heat-treating at 100 ° C. for 30 seconds. A gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) was formed.

[Example 3]
300 Å thick aluminum oxide was formed under the following deposition conditions by physicochemical vapor deposition using a vacuum deposition apparatus on the base material, and 35.0 parts by weight of natural zeolite having a particle size of 10 μm was used as the desiccant. Except for this, the oxygen-water-absorbing pouch and packaged product of the present invention were produced in the same manner as in Example 2.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2.0 × 10 ⁻⁴ mbar
Degree of vacuum in the winding chamber: 2 × 10 ^-2 mbar
Film transport speed: 300 m / min Electron beam power: 25 kW

[Example 4]
The oxygen-water-absorbing pouch and packaged product of the present invention were produced in the same manner as in Example 3 except that 40.0 parts by weight of molecular sieve having a particle size of 5 μm was used as the desiccant.

[Example 5]
1. Manufacture of Oxygen-Moisture Absorbent Laminate (1) Manufacture of Oxygen-Moisture Absorbent Resin Film First, the following resin compositions (a) to (c) were prepared.
(A) First layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight and synthetic silica 0.5 weight Part, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylene bisoleic acid amide were sufficiently kneaded to prepare a resin composition forming the first layer.

(B) Second layer As the oxidizing resin, [ethylene / methyl acrylate / methylcyclohexene methyl acrylate copolymer] 100.0 parts by weight, and as the transition metal catalyst, [cobalt 2-ethylhexanoate] 0.01 parts by weight Then, 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] as a radical photopolymerization initiator was sufficiently kneaded to prepare a resin composition for forming the second layer.

(C) Third layer High pressure method low density polyethylene [HPLDPE, density: 0.923 g / m ³ , melt flow rate (MFR): 3.5 g / 10 min] 100.0 parts by weight, and synthetic silica 0.5 weight Part and 35.0 parts by weight of natural zeolite having a particle size of 10 μm were sufficiently kneaded to prepare a resin composition forming the third layer.

  Next, using the resin compositions (a) to (c) prepared above, and using an air-blowing co-extrusion film forming machine for blowing these, the first layer of the resin composition of (a) is 10 μm, The oxygen moisture-absorbing resin film was manufactured by co-extrusion so that the second layer of the resin composition of (b) was 10 μm and the third layer of the resin composition of (c) was 30 μm.

(2) Formation of barrier thin film layer and gas barrier coating film on substrate film A biaxially stretched polyethylene terephthalate film is used as the substrate film. Mounted on the delivery roll. Next, this was drawn out, and a 300-nm thick aluminum oxide vapor deposition film was formed as a barrier thin film layer on the biaxially stretched polyethylene terephthalate film by the physical chemical vapor deposition method under the following vapor deposition conditions.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2.0 × 10 ⁻⁴ mbar
Degree of vacuum in the winding chamber: 2 × 10 ^-2 mbar
Film transport speed: 300 m / min Electron beam power: 25 kW

Further, a glow discharge plasma generator is used on the surface of the vapor deposition film of aluminum oxide, and the mixture is 9 kw in power and oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm). Using gas, oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 8.0 × 10 ⁻⁵ mbar and a treatment speed of 100 m / min to improve the surface tension of the deposited film surface of organic silicon oxide by 54 dyne / cm or more. A plasma treated surface was formed.
On the other hand, according to the composition shown in the following (Table 2), the prepared composition a. A pre-prepared composition b. In a mixed solution comprising an aqueous polyvinyl alcohol solution, isopropyl alcohol and ion-exchanged water. A hydrolyzed solution consisting of ethyl silicate, silane coupling agent, isopropyl alcohol, 0.5N hydrochloric acid aqueous solution and ion-exchanged water was added and stirred sufficiently to obtain a colorless and transparent barrier coating solution.

  Next, the gas barrier composition produced above is used for the plasma treatment surface of the aluminum oxide vapor deposition film formed in (1) above, and this is coated by the gravure roll coating method, and then at 100 ° C. A heat treatment was performed for 30 seconds to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state).

(3) Manufacture of oxygen-water-absorbing laminate A two-component curable urethane-based adhesive is applied to the gas barrier coating film surface of the base film on which the barrier thin film layer and the gas barrier coating film manufactured in (2) are formed. Then, by the gravure roll coat method, it is laminated so as to be 4.0 g / m ² in a dry state, and is bonded to the surface on which the first layer of the oxygen moisture absorbing resin film is formed, and the oxygen moisture absorbing laminate is obtained. Manufactured.

2. Production of oxygen moisture-absorbing pouches and packaging products Prepare two sheets of oxygen-moisture-absorbing laminate produced as described above, superimpose them so that the surfaces of the oxygen-moisture-absorbing resin film face each other, and end the periphery around the three sides The oxygen-water-absorbing pouch of the present invention comprising a three-side-sealed soft packaging bag having an opening at the top was formed by heat sealing.
Furthermore, using an ultraviolet ray irradiation device [manufactured by Eye Graphics, model: ECS-401GX], an ultraviolet ray of 1000 mJ / cm ² is irradiated on the inner surface of the oxygen moisture absorbing pouch produced as described above, and a printed circuit board is placed. The opening part was heat-sealed to form an upper seal part to produce the packaged product of the present invention.

[Experimental example]
1. Measurement of Oxygen Permeability and Water Vapor Permeability The oxygen permeability and water vapor permeability of the base material provided with the gas barrier layer produced in Examples 1 to 5 or the gas barrier layer and the gas barrier coating film are as follows. It was measured.
Oxygen permeability: Measured with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH (JIS standard K7126).
Water vapor permeability: 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 (JIS standard K7129).
The results are shown below (Table 3).

As described above (Table 3), the gas barrier layer produced in Examples 1 to 5 or the base material provided with the gas barrier layer and the gas barrier coating film has excellent oxygen permeability and water vapor permeability. Was confirmed. In particular, the oxygen permeability and water vapor permeability of the base material of Example 2 provided with a gas barrier coating film were 0.3 (cc / m ² .day.atm) and 0.4 (g / m ² .day), respectively. On the other hand, the oxygen permeability and water vapor permeability of the base material of Example 1 in which the gas barrier coating film was not provided were 1.5 (cc / m ² .day.atm), 1.4 ( g / m ² .day) and slightly higher, by providing a gas barrier coating film, it was confirmed that the gas barrier properties such as oxygen barrier properties and water vapor barrier property is further improved.

2. Measurement of Oxygen Absorption A 100 mm × 100 mm test piece of the oxygen-absorbing laminate produced in Examples 1 to 4 or the oxygen-moisture-absorbing laminate produced in Example 5 was irradiated with 1000 mJ / cm ² ultraviolet light. . Next, the test piece was placed in a 130 mm × 170 mm aluminum pouch, and 100 mL of air was further injected and sealed.
After 5 days, the oxygen concentration in the pouch was measured with an oxygen concentration meter [manufactured by Toray Engineering Co., Ltd., model name: LC-750F], and the oxygen absorption amount of the oxygen-absorbing laminate or oxygen-moisture-absorbing laminate was measured. Evaluated.
The results are shown below (Table 4).

  As described above (Table 4), it was confirmed that the oxygen-absorbing laminate produced in Examples 1 to 4 or the oxygen-moisture-absorbing laminate produced in Example 5 had excellent oxygen absorption performance. It was.

3. Measurement of moisture-absorbable amount A 100 mm × 100 mm test piece of the moisture-absorbing laminate produced in Examples 1 to 4 or the oxygen-moisture-absorbing laminate produced in Example 5 was used at 40 ° C. and 90% high temperature and humidity. When the weight of the test piece was measured after 7 days, 14 days, and 28 days after entering the room, it was confirmed that a saturated state was reached after 14 days.
Therefore, the moisture absorption amount of each test piece after 14 days is shown in the following (Table 5) as a moisture absorption possible amount.

  As described above (Table 5), it was confirmed that the moisture-absorbing laminate produced in Examples 1 to 4 or the oxygen-moisture-absorbing laminate produced in Example 5 had excellent moisture absorption performance. It was.

4). Preservation test The packaging product of the present invention containing the printed circuit boards manufactured in Examples 1 to 5 above was stored for one year, and the performance of the printed circuit board as a content was compared before and after storage. First, it was confirmed that the oxygen-moisture-absorbing pouch of the present invention has extremely good storage characteristics.

It is a schematic sectional drawing which shows an example of the layer structure about the water | moisture-content laminated body which comprises the oxygen moisture absorption pouch of this invention. It is a schematic sectional drawing which shows an example of the layer structure about the water | moisture-content laminated body which comprises the oxygen moisture absorption pouch of this invention. It is a schematic sectional drawing which shows an example of the layer structure about the water | moisture-content laminated body which comprises the oxygen moisture absorption pouch of this invention. It is a schematic sectional drawing which shows an example of the layer structure about the oxygen absorption laminated body which comprises the oxygen moisture absorption pouch of this invention. It is a schematic sectional drawing which shows an example of the layer structure about the oxygen moisture absorption laminated body which comprises the oxygen moisture absorption pouch of this invention. It is a schematic perspective view which shows an example of a structure of the oxygen moisture absorptive pouch of this invention manufactured by bag-making using the laminated body shown in FIG. 1, FIG. It is a schematic perspective view which shows the example about the packaging product which filled and packaged the content in the oxygen moisture absorption pouch of this invention shown in the said FIG. It is a schematic perspective view which shows the example about the packaging product which filled and packaged the content in the oxygen moisture absorption pouch of this invention shown in the said FIG. 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Barrier thin film layer 3 Water-absorbing resin film 3a Water-absorbing resin layer 3b, 3b 'Heat-sealable resin layer 4 Heat-sealable resin film 5 Two-layer coextrusion multilayer laminated film 6 Three-layer coextrusion multilayer Laminated film 7 Oxygen absorbing resin film 11 Heat seal part 12 Opening part 13 Ultraviolet irradiation device 14 Ultraviolet light 15 Contents 16 Upper seal part 21 Plasma chemical vapor deposition apparatus 22 Vacuum chamber 23 Unwinding roll 24 Auxiliary roll 25 Cooling / electrode Drums 26 and 27 Gas supply device 28 Raw material volatilization supply device 29 Raw material supply nozzle 30 Glow discharge plasma 31 Power source 32 Magnet 33 Guide roll 34 Winding roll 40 Winding type vacuum deposition device 41 Winding chamber 42 Winding rolls 43 and 44 Guide Roll 45 Coating drum 46 Deposition source 47 Oxygen gas outlet 48 Mask 49, 50 Guide roll 51 Winding roll 52 Crucible 53 Deposition chamber A ₁ Moisture absorbing laminate A ₂ Moisture absorbing laminate A ₃ Moisture absorbing laminate B Oxygen absorbing laminate C Oxygen moisture absorbing laminate D Oxygen moisture absorbing pouch E Packaging product P Direction of movement of UV irradiation device

Claims (11)

An oxygen moisture absorbing pouch using a moisture absorbing laminate and an oxygen absorbing laminate,
a) the moisture-absorbing laminate comprises a moisture-absorbing resin film comprising a resin composition containing (i) a base film, (ii) a barrier thin film layer, and (iii) a desiccant,
b) The oxygen-absorbing laminate comprises an oxygen-absorbing resin film comprising (i) a base film, (ii) a barrier thin film layer, and (iii) a resin composition containing an oxidizing resin and a transition metal catalyst. And c) an oxygen-moisture-absorbing pouch, wherein the bag is formed so that the moisture-absorbing resin film surface and the oxygen-absorbing resin film surface face each other.   The moisture-absorbing resin film comprises a moisture-absorbing resin layer comprising a resin composition comprising a thermoplastic resin containing a desiccant as a main component of the vehicle, and a heat comprising a resin composition comprising the thermoplastic resin as a main component of the vehicle. The oxygen-water-absorbing pouch according to claim 1, comprising two layers including a sealing resin layer.   The moisture-absorbing resin film is composed of a heat-sealable resin layer made of a resin composition containing a thermoplastic resin as a main component of the vehicle, and a moisture consisting of a resin composition containing a thermoplastic resin containing a desiccant as the main component of the vehicle. The oxygen-moisture-absorbing property according to claim 1, comprising three layers in which an absorbent resin layer and a heat-sealable resin layer made of a resin composition containing a thermoplastic resin as a main component of the vehicle are sequentially laminated. Pouch.   The oxygen-absorbing resin film is composed of two layers, an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, and a heat-sealable resin layer made of a resin composition containing a thermoplastic resin as a main component of the vehicle. The oxygen-moisture-absorbing pouch according to any one of claims 1 to 3.   The oxygen-absorbing resin film comprises a heat-sealable resin layer comprising a resin composition containing a thermoplastic resin as a main component of the vehicle, an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, and a thermoplastic resin as a vehicle. The oxygen-water-absorbing pouch according to any one of claims 1 to 3, wherein the oxygen-water-absorbing pouch comprises three layers in which a heat-sealable resin layer made of a resin composition as a main component is laminated in order. An oxygen moisture absorbing pouch using an oxygen moisture absorbing laminate comprising a base film, a barrier thin film layer, and an oxygen moisture absorbing resin film,
The oxygen moisture-absorbing resin film comprises a heat-sealable resin layer made of a resin composition containing a thermoplastic resin as a main component of a vehicle, an oxygen-absorbing resin layer containing an oxidizing resin and a transition metal catalyst, and a desiccant. An oxygen moisture-absorbing pouch comprising three layers in which a moisture-absorbing resin layer comprising a resin composition containing a thermoplastic resin as a main component of a vehicle is laminated in order.   The oxygen moisture-absorbing pouch according to any one of claims 1 to 6, wherein the desiccant is at least one selected from the group consisting of zeolite, molecular sieve, silica gel, and activated alumina.   The barrier thin film layer is made of a vapor-deposited film of organic silicon oxide by a chemical vapor deposition method or a vapor-deposited film of inorganic oxide by a vacuum vapor deposition method. Oxygen moisture-absorbing pouch. An oxygen moisture absorbing pouch provided with a gas barrier coating film on a barrier thin film layer,
The gas barrier coating film has a general formula R ¹ _n M (OR ₂ ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, 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), a polyvinyl alcohol-based resin, and / or Or an ethylene-vinyl alcohol copolymer, and a gas barrier composition that is polycondensed by the sol-gel method in the presence of a sol-gel method catalyst, water, and an organic solvent. The oxygen-moisture-absorbing pouch according to any one of claims 1 to 8.   The resin composition used for the oxygen-absorbing resin layer further contains one or more additives selected from the group consisting of a binder, a radical generator and a photosensitizer. The oxygen moisture-absorbing pouch according to any one of the above.   Before filling the oxygen moisture-absorbing pouch according to any one of claims 1 to 10 with contents, after filling or simultaneously with filling, the inner surface of the pouch is irradiated with ultraviolet rays, and the opening of the pouch is opened. A packaged product that is hermetically sealed by heat sealing.

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