JP2001287752A - Bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bag having a superior oxygen barrier or moisture-proof effect in which, even if either moisture or oxygen is increased, a packaging member has a transparent portion through which variation in either contents or indicator can be seen. SOLUTION: A bag 20 is comprised of a laminated film 10 including a transparent barrier film 12 having a thin film composed of non-organic oxide 2 on at least a substrate film 1, non-transparent portions 41(A), 42(A) and 41(C) having a metallic foil 4 laminated partially on the barrier film, and a transparent segment 6 not including any metallic foil and an HS layer 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bag made of a plastic film as a base material, and prevents the penetration of moisture that causes deterioration even in the presence of electronic components such as sophisticated integrated circuits and semiconductors, or even in a very small amount. In addition, it belongs to an ultra-high-barrier bag provided with a transparent portion that allows the user to visually recognize the change status of a humidity detector (indicator) that changes or changes color due to moisture or oxygen.

[0002]

2. Description of the Related Art Conventional integrated circuits, electronic parts such as semiconductors, and the like, for example, even if the package contains a very small amount of oxygen or moisture,
If present, the copper plate was oxidized or corroded, causing deterioration of solder wettability. Further, when a harmful gas such as hydrogen sulfide, sulfurous acid gas or ammonia gas permeates from the outside, there is a problem that the copper plate is oxidized or corroded. In such a case, a bag for preventing penetration of moisture and harmful gas has been used by forming a bag having a shape according to the purpose by using a multilayer film composed of a laminate including a metal aluminum foil as a component. . However, although multilayer films containing metal foils are very good in terms of barrier properties such as moisture resistance, the opacity of the metal foils makes it impossible to identify changes in the packaged contents, and in particular, it is enclosed in a package. However, there is a problem that it is not possible to recognize a change in an indicator for recognizing a change in moisture or oxygen.

Instead of a metal foil, an ordinary barrier film having a transparent and excellent moisture-proof effect, for example, a vinylidene chloride coated film, silicon oxide (hereinafter referred to as SiO _x ), aluminum oxide (AlO _x ), yttrium oxide It has also been attempted to use a transparent film on which an inorganic substance such as (YO _x ) has been deposited. However, there is a problem that the barrier effect is inferior to that of a metal foil, and that a film treated with a chlorine compound generates harmful substances when the waste is treated.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to a transparent portion which is excellent in barrier properties such as a moisture-proof effect, and which can recognize a change in contents or indicators when the content of a package or moisture increases due to an increase in moisture or oxygen. It is an object of the present invention to provide a bag having the same.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention provides a transparent barrier film in which at least a base film is coated with a thin film made of an inorganic oxide over the entire surface;
A bag formed of a laminate film of a heat sealant layer (hereinafter, referred to as an HS layer) and an opaque portion in which a metal foil is partially formed on the barrier film and a transparent portion not containing the metal foil. . Further, the thin film is made of SiO
It is a bag made of _x deposited film. The metal foil is a bag made of metal aluminum.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIGS. 1A and 1B, a bag according to the present invention is a transparent barrier comprising at least a base film 1 and a thin film 2 made of an inorganic oxide applied to the entire surface. A film 12 and a metal foil 4 partially on the barrier film.
20 formed by laminating a laminated film 10 composed of a partially opaque portion 41A, 42A and 41B, a transparent portion 6 not including a metal foil, and an HS layer 5 with an HS portion 7
It is. The thin film 2 is a bag 20 made of a deposited SiO _x film. The metal foil 4 is a bag 20 made of metal aluminum.

The base film on which the inorganic oxide of the present invention is provided is made of polyolefin resin such as polyethylene or polypropylene, polystyrene, polyamide, acrylic resin containing acrylic acid ester or methacrylic acid ester as a main component, polyethylene terephthalate, polybutylene terephthalate. And a stretched or non-stretched film made of polyester such as polyethylene naphthalate, polyacetal, cellulose di-, or triacetate. The thickness depends on the size of the bag, the shape and density of the contents, and is 5 to 100 μm. The preferred thickness is 7 to 35 μm from the viewpoint of handling of contents and processing.
m. Stretched films of polyethylene terephthalate and polyamide can be used preferably from the point of strength, and polypropylene films can be used from the point of moisture-proof effect. In addition, for the purpose of adding stability to the work when manufacturing a film from the above-mentioned resin and properties of the film, an antioxidant property, an ultraviolet ray preventive property,
Various additives (chemicals) for improving the slip property, antistatic property, etc. may be added to the resin in an amount up to 10 parts according to the purpose, or a transparent pigment or dye may be added for the purpose of coloring. It can also be colored.

The substrate film used in the present invention is subjected to a physical or chemical surface treatment for the purpose of firmly stabilizing the adhesiveness with an inorganic oxide to be deposited for forming a thin film as described below. Is preferred. For example, corona discharge treatment,
There are physical surface treatment such as plasma treatment, ozone gas treatment, and oxidation treatment with chemicals. Further, the physical treatment surface may be selected from polyester, polyurethane, polyurethane isocyanate, epoxy resin and the like and subjected to a primer treatment by coating to stabilize the adhesion.

The inorganic oxide forming the vapor-deposited film of the present invention comprises:
It can be performed by a chemical vapor deposition method (chemical vapor deposition method: CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photothermal chemical vapor deposition method. In addition, a deposited film of an inorganic oxide can be formed by a physical vapor deposition method (physical vapor deposition method: PVD method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. Specifically, a vacuum deposition method in which an inorganic oxide is used as a raw material, which is heated and vaporized, and vapor-deposited, and an oxidation reaction deposition method in which an inorganic oxide is used as a raw material and oxygen is introduced and oxidized to be deposited on a base film. Further, a vapor-deposited film can be formed by using a plasma-assisted oxidation reaction vapor deposition method in which an oxidation reaction is promoted by plasma. The deposition material can be heated and vaporized by a resistance heating method, a high-frequency induction heating method, an electron beam heating method, or the like.

The inorganic oxide used in the present invention is basically usable as long as it can form a thin film by vapor-depositing an inorganic oxide containing silicon. For example, silicon or an oxide of aluminum, magnesium, tin, boron, titanium, yttrium, zirconium, or the like (MOx: where M represents an inorganic element and O represents oxygen) can be used. And x
Range of silicon is 2 or less and aluminum is 1.5 or less.
Hereinafter, magnesium is 1 or less, tin is 2 or less, boron is 1.5 or less, titanium is 2 or less, yttrium is 1.5 or less, and zirconium is 2 or less. And when x is 0, it is a completely metal or inorganic substance and becomes an opaque film. The upper limit of x is a completely oxidized oxide. In the present invention, silicon and aluminum are generally used, and the range of x is 0.5 to 2.0 for silicon and 0.5 to 1.5 for aluminum.
Those in the range are preferably used. The thickness of the inorganic oxide varies depending on the inorganic substance used, but is 50 to 200.
It is in the range of 0 °, preferably in the range of 100-1000 °. In the present invention, the thin film formed by vapor deposition of MOx is a metal to be used, or a metal oxide or a mixture of two or more metal oxides or an inorganic oxide vapor-deposited film mixed with different materials. Can be configured.

In the present invention, the inorganic oxide vapor-deposited film provided on the barrier film is formed by forming one of the above-mentioned PVD method and CVD method or a combination film of two or more different layers by using both of them. Can also be used. And
The method for forming a composite film composed of two or more layers of the above-mentioned different types of inorganic oxides includes a method of forming an inorganic oxide which is dense, highly flexible, and capable of preventing cracks from being formed on a substrate film by a CVD method. It is also possible to form a composite vapor-deposited film of two or more layers in which a film is provided and then a vapor-deposited inorganic oxide film is formed by a PVD method.

A vapor-deposited film of an inorganic oxide such as SiO _x is formed by using a gaseous vapor-deposition monomer such as an organic silicon compound as a raw material on the side of the substrate film on which the adhesion strengthening treatment has been performed, and using a gas such as argon or helium gas. A low-temperature plasma-enhanced chemical vapor deposition method can be formed using an active gas and a low-temperature plasma generator together with oxygen gas for supply. Examples of the low-temperature plasma generator include high-frequency plasma, pulse wave plasma, and microwave plasma. In the present invention, it is preferable to use a high-frequency plasma method capable of generating stable plasma with high activity.

In the present invention, a first layer of an inorganic oxide vapor-deposited film is first formed by using the above-described low-temperature plasma-enhanced chemical vapor deposition apparatus, and then a vapor-deposited film of the first layer is formed in the same manner. A second inorganic oxide deposited film can be formed, or a similar low-temperature plasma enhanced chemical vapor deposition apparatus can be connected in a double system to continuously form an inorganic oxide deposited film. . By repeating this, a deposited film of two or more inorganic oxides having different components can be formed.

[0014] Monomers for depositing an organosilicon compound for forming a deposited film of an inorganic oxide of SiO _x by a CVD method include tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, and the like. Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, octamethylcyclotetrasiloxane And one or more of these can be selected and used. In the present invention, among the above-mentioned organosilicon compounds, tetramethyldisiloxane is a preferable material in view of handleability and characteristics of the formed deposited film. And, as the inert gas, argon, helium or the like can be preferably used.

The SiO _x formed by a chemical reaction between a monomer such as an organosilicon compound and oxygen gas by the above method.
Is a film in which SiO _{x having} a value of 2 or less is densely adhered firmly to the substrate film and is dense and highly flexible. The SiO _x deposited film is preferably x from the viewpoint of transparency, barrier properties such as water vapor and oxygen.
Are 1.3 to 1.9. _X of the above SiO x
Varies depending on the molar ratio of monomer to oxygen, the energy of plasma, and the like.Generally, as the value of x decreases, the gas permeability decreases, but the deposited film becomes yellowish and the transparency decreases. Will be. In addition, the SiO _x is essential to be composed of silicon and an oxygen element, and in addition, is composed of a vapor-deposited film containing one of carbon and hydrogen, or both elements as trace elements, The ratio between the element and the trace element is continuously decreasing in the film thickness direction. And the thickness of the deposited film is 50-40.
00 °, specifically 100 to 1000 °. When the thickness exceeds 1000 °, the barrier properties are excellent, but cracks easily occur. Therefore, it is preferable to select the thickness in consideration of the rigidity of the base film. When the angle is less than 100 °, the transparency is excellent but the barrier property may be reduced. When it is desired to change the thickness of the SiO _x , the volume velocity of the deposited film is increased, that is,
It can be performed by a method such as increasing the amount of the monomer and oxygen to increase the thickness or decreasing the deposition rate to decrease the thickness.

In the method of forming a vapor-deposited film of an inorganic oxide of the present invention by a PVD method, the inorganic oxide is used as a raw material, which is heated to form a vapor on one side of a base film. There is a vacuum deposition method and the like. The heating of the deposition material includes a resistance heating method, a high-frequency induction heating method, an electron beam heating method, and the like.

The deposited film of the inorganic oxide applied to the present invention is:
It can be formed by either the CVD method or the PVD method, but it is also possible to use both by forming a composite vapor-deposited film of two or more layers made of different inorganic oxides by using both of them. When the two types of inorganic oxides are formed in two layers as described above, the base film is provided with an inorganic oxide that is dense, highly flexible and relatively hard to crack by a CVD method, and is further provided with a PVD method. It is preferable to provide a denser vapor-deposited film formed of an inorganic oxide according to the above, and to form a dense vapor-deposited film that is less likely to generate cracks composed of two or more layers. Of course, the above two-layer structure is reversed, and the substrate film is first subjected to the PVD method,
By providing a vapor-deposited film by a method, a structure that is dense and rich in flexibility and relatively hardly generates cracks can be used.

It is preferable that the metal foil has a light shielding property and is excellent in flexibility even when a laminated film is formed. Flexible from aluminum, iron, brass etc., especially rolling,
It is preferable that the thickness of the degreased and annealed soft aluminum excellent in laminating processability is 7 to 30 μm, and a pinhole is less likely to be generated when a bag is formed and then bent in a distribution process or the like.

The HS layer can be appropriately selected from a thermoplastic resin capable of heat sealing (hereinafter referred to as HS) and a material capable of being processed into a film. For example, polyamide,
Polyester, polyethylene, polypropylene, copolymer of ethylene and vinyl acetate, and ethylene and acrylic acid,
There is an acrylic resin made of a copolymer with methacrylic acid or an ester thereof. Preferably, it is a linear polyethylene (LLDPE) which is a copolymer of ethylene and an α-olefin. It is preferable to add an antistatic agent such as a surfactant so that the HS layer of the present invention does not generate static electricity by contacting the contents. Also, H
From the standpoint of preventing the S layer from being charged, a saponified product of a copolymer of ethylene and vinyl acetate, which is a copolymer of ethylene and vinyl alcohol, can also be used. The saponified product preferably has an ethylene content of 50% or more by mole of ethylene whose HS property is stable.

When laminating the base film and the aluminum foil, two or more rows of the base film having a width of 1/2 or less are used so that a transparent section is formed in the processing direction of the film. As described above, the opaque portions are formed in two or more rows.
The width of the transparent portion should be large enough to identify the contents of the bag. If the transparent portion is made wider than necessary, the characteristics of the metal foil constituting the bag of the present invention cannot be utilized, and the barrier properties will be relatively reduced. Conversely, if the transparent portion is narrowed, the reduction in barrier properties can be reduced, but not only the identification of the contents becomes difficult, but also when the base film and the metal foil are laminated, the metal foils are in contact with each other, or The transparent portions cannot be formed due to the lamination. Although it depends on the accuracy of the processing machine and the shape and size of the bag, it is preferable to set a transparent portion having a width of 10 mm or more.

The lamination processing of the base film and the metal foil such as an aluminum foil is performed by sandwich lamination using a thermoplastic resin as an adhesive resin layer by using a usual melt extrusion laminator. The metal foil is cut to a desired width, and a hot-melt adhesive resin is applied to the base film, and the metal foil is pressed and laminated on the adhesive resin. Further, the laminated film of the present invention is formed by melt-extruding and coating a thermoplastic resin to be an HS layer, or by performing dry lamination using an adhesive. The lamination side of the base film and the metal foil is preferably performed on the side on which the deposited film is provided. This is preferable also from the viewpoint of preventing damage in the subsequent steps from the adhesive resin layer formed in the first step, which is a relatively brittle and easily breakable deposited film.
In addition, a primer treatment may be applied to the adhesive resin layer and the metal foil on the side where the base film is laminated with the metal foil such as aluminum and the side where the HS layer is further laminated on the surface where the metal foil is laminated, if necessary. Can be.

The primer used for the above lamination can be selected from those which can be used for sandwich lamination using a usual thermoplastic resin. For example, there are an organic titanium compound polyisocyanate, a polyester isocyanate, and a polyurethane isocyanate.

The adhesive resin layer is made of polyethylene or ethylene.
Vinyl acetate copolymer, ethylene / acrylic acid copolymer,
Ethylene / acrylate copolymers, ionomers, and the like can be used, and among them, copolymers with acrylic acid are preferred because they exhibit strong chemical adhesion to metal foil.

The processing of the laminated film used for the bag of the present invention can be performed by a so-called dry lamination using a reaction-curable adhesive, in addition to the method of performing a sandwich lamination using a thermoplastic resin as an adhesive resin layer. it can. After applying an adhesive to the vapor deposition film side of the barrier film, a metal foil is laminated. Then, if necessary, an adhesive is applied after performing an easy-adhesion treatment such as a corona discharge treatment, and then the film to be the HS layer is dry-laminated, or the resin of the HS layer is directly melt-extruded and coated to form a laminate. Is what you do.

In the method by dry lamination using an adhesive, an adhesive is applied to the treated surface of oriented polypropylene, a metal foil is laminated (first step), and an adhesive is further applied to form a film of the HS layer. This is an interesting processing method when laminating (second step). Because, after the first step, the non-laminated surface of the base film is not subjected to corona treatment even if it is wound up. By selecting an agent, the risk of causing blocking can be reduced even when wound up by lamination with a metal foil. In addition, the dry laminator can perform low-temperature processing with a simpler machine than an adhesive resin extrusion coater, and has an advantage that the width of the transparent portion can be accurately adjusted.

The shape of the package can be any shape according to the shape and size of the contents to be packaged, such as a gusset bag and a three-side seal bag, in addition to the four-side seal bag shown in the figure. The transparent portion may be at the center or the side of the bag, and may have a plurality of transparent portions.

[0027]

EXAMPLE (Example 1) As shown in FIG.
A barrier film 12 was formed by applying a vapor-deposited film 2 of SiO _{x to} a biaxially oriented polypropylene film (base film 1) having a width of 500 μm and a width of 500 mm. Next, a primer 16 made of a polyester / isocyanate resin is applied to the side of the vapor-deposited film 2 of the barrier film 12 by a tandem type melt extrusion coater, and the ethylene / acrylic acid copolymer is hot-melt-extruded to a thickness of 20 μm and simultaneously coated with a thickness 15μm 180mm width, 120mm width, and 180m
As shown in FIG. 2A, aluminum foils 41, 42 and 43 having a width of m are arranged in three rows at intervals of 20 mm. And
Transparent parts 61 and 6 shown in FIGS. 2B and 2C.
2, and opaque portions 41A and 42 located on the surface of the bag body
A, 42B, 43A and an aluminum foil were arranged so as to have opaque portions 41B, 43B located on the back surface of the bag body, and laminated by sandwich lamination via the adhesive resin layer 3. Next, a 30 μm-thick linear polyethylene was melt-extruded and coated on the metal foil 4 and the adhesive resin layer 3 side to form an HS layer 5, thereby producing a laminated film 10 of the present invention. The laminated film 10 is slit in two rows at the cutting position 8 and the HS layer is folded in two at the folding position 9A so as to face the HS layer, as shown in FIG. 2 (C). HS having a height of 180 mm and a width of 120 mm with the opaque portion 41B on the rear side
HS was performed in the part 7 to form a bag 20A having a transparent part 61. In the same manner, the folding position 9
2B, the HS layer is folded in two, and the HS layer 7 is subjected to HS. Then, as shown in FIG. 2C, the same size having the transparent portion 62, the opaque portions 42B and 43A, and the opaque portion 43B on the back surface is formed. A bag 20B was created.

Example 2 A bag 20 of Example 2 was prepared in the same manner as in Example 1 except that a biaxially oriented polyester film having a thickness of 12 μm was used instead of the biaxially oriented polypropylene film used in Example 1. Created.

Example 3 Instead of the biaxially oriented polypropylene film used in Example 1, a 25 μm-thick biaxially oriented nylon film 6, 6 film was used, and the adhesive resin layer was made of an ethylene / acrylic acid copolymer. The bag 2 of the third embodiment having the transparent portion 61 in the same manner as the first embodiment except that
0 was created.

Comparative Example 1 A bag of Comparative Example 1 having no transparent portion was prepared in the same manner as in Example 2 except that the aluminum foil of Example 2 was provided on the entire surface.

(Comparative Example 2) A bag of Comparative Example 2 was formed in the same manner as in Example 2 except that the aluminum foil was omitted.

Next, for the bags of Examples 1 to 3 and Comparative Examples 1 and 2, JIS K7129 “Method for testing water vapor permeability of plastic films and sheets” and JIS
Table 1 shows the measurement results of the moisture permeability and the oxygen permeability measured and evaluated in accordance with K7126 "Test method for gas permeability of plastic films and sheets".

[0033]

[Table 1]

[0034]

As described above, a bag made of a composite film in which a metal foil having a super barrier property is laminated in a stripe shape on a barrier film which is transparent and has an excellent barrier property against water vapor and oxygen gas, has a content and a packaging. In addition to being able to identify changes in oxygen and water vapor inside the body, there is an effect that a bag excellent in barrier properties can be formed comprehensively.

[Brief description of the drawings]

FIG. 1A shows a layer structure of a laminated film having a transparent portion. (B) It is a key map showing an example of a bag which has a transparent part.

FIG. 2A is a conceptual diagram showing a cross section of a laminated film of an example. (B) It is a key map showing the plane of a lamination film of an example. (C) It is a perspective view showing the concept of the bag of an example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Base film 2 Thin film 3 Adhesive resin layer 4 Metal foil 5 HS layer 6, 61, 62 Transparent part 7 HS part 8 Cutting position 9A 9B Folding part 10 Laminated film 12 Barrier film 16 Primer 20, 20A, 20B Bag 41, 42, 43 Aluminum foil 41A, 41B, 42A, 42B, 43A, 43B Opaque part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 23:00 C08L 23:00 F term (Reference) 3E064 AA01 BA22 BB03 BC08 FA01 HH05 4F006 AA12 AA35 AA38 AB74 AB76 BA05 CA07 DA01 4F100 AA17B AA20B AB10C AB33C AK01A AK07 AK63 AK70 AT00A BA04 BA07 BA10A CB03D CB03G DA01 DC21C DC22 EH23 EH66B EJ38 GB15 JD01 JL12D JL12G JN01 JN01C JN02

Claims (3)

[Claims] 1. A transparent barrier film in which at least a base film is coated with a thin film made of an inorganic oxide over the entire surface;
A bag comprising a laminated film of a heat sealant layer and an opaque portion in which a metal foil is partially formed on the barrier film and a transparent portion not containing the metal foil. 2. The bag according to claim 1, wherein said thin film is a deposited film made of silicon oxide. 3. The bag according to claim 1, wherein the metal foil is aluminum metal.