JP3139322B2 - Camera packaging - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a camera package in which a camera body containing a photosensitive material in advance is packaged using a transparent and laminated film containing a barrier material having excellent gas barrier properties.

[0002]

2. Description of the Related Art In recent years, cameras containing photosensitive materials in advance have become very popular because they can be used easily.
In this camera, since the photosensitive material is stored in advance, it is necessary to stably protect the stored photosensitive material from the time of manufacture to the time of use by the consumer. Therefore, as a packaging material for packaging the camera, a laminated material including an aluminum foil, which is excellent in gas barrier properties such as moisture resistance, has been generally used.

[0003] However, since the aluminum foil is an opaque material, the packaged camera cannot be seen through the exterior body. Further, the above-mentioned outer package of the camera package is discarded after use. However, since the exterior body is a laminated material including aluminum foil as described above, there is a problem that the aluminum foil remains without burning even after incineration.

On the other hand, in order to solve such a problem of disposal, instead of a laminated material using aluminum foil,
A camera package using a laminated material including a glass vapor-deposited film (a vapor-deposited film on which silicon oxide is vapor-deposited) has been proposed (JP-A-3-243946). The above-mentioned vapor-deposited film is a material which is transparent and has good gas barrier properties, but has the following points to be improved.

[0005]

In the case of a camera containing a photosensitive material in advance, a particularly high moisture-proof property is required, specifically, a water vapor barrier property of 0.3 g / m ² or less.

Further, as described above, silicon monoxide (S
silicon oxide such as iO), magnesium oxide (MgO)
A deposited film provided by depositing an inorganic compound such as
The thin film of the inorganic compound used for the gas barrier layer lacks flexibility, is susceptible to rubbing and bending, and has poor adhesion to the base material, so care must be taken in handling, especially the adhesion layer on the vapor deposition film When another film is laminated through the film, the gas barrier property is remarkably reduced, and there is a problem that the above conditions cannot be satisfied.

Accordingly, the present invention makes it possible to preserve the stored photosensitive material by packaging it with an outer package using a barrier material having flexibility and excellent gas barrier properties against oxygen, water vapor and the like. It is intended to provide a camera package.

[0008]

According to a first aspect of the present invention, there is provided a camera package in which a camera body preliminarily containing a photosensitive material is hermetically packaged with an exterior body made of a moisture-proof film. Containing a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof on the evaporation surface of an evaporation film provided with an inorganic compound evaporation layer having a film thickness of 50 to 3000 °
A camera package comprising a laminated film having a barrier material provided with a coating layer having a thickness of 0.01 to 50 μm .

According to a second aspect of the present invention, a water-soluble polymer of the first aspect of the invention and a metal alkoxide or a hydrolyzate thereof are replaced with a coating layer having a thickness of 0.01 to 50 μm , A camera package comprising a barrier material containing tin chloride and having a coating layer having a thickness of 0.01 to 50 μm .

In the above-mentioned invention, it is preferable to use a substrate having an anchor coat layer for vapor-depositing an inorganic compound on a vapor deposition surface as a substrate of the barrier material.

It is preferable to use, as the outer package, a laminated film provided with an outer package made of a petitstick film on the side opposite to the vapor deposition layer of the substrate.

[0012]

According to the present invention, the exterior body is provided with an inorganic compound vapor deposited layer, a coating layer of a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof, or a coating layer of a water-soluble polymer and tin oxide on a substrate. Since it is composed of a laminated film having a barrier material, it has sufficient barrier properties even when the thickness of the vapor-deposited layer is small, and is affected by the components of the adhesive in the manufacturing process of the outer package (laminated film) or the adhesive layer. Pinholes, cracks, and the like generated in the deposited layer due to the influence of the formation can be prevented.

[0013] Further, in the process of packaging the camera body with the exterior body, the occurrence of pinholes and cracks in the vapor-deposited layer caused by bending or sealing is reduced, and the barrier properties of the exterior body can be maintained.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described in detail. FIG.
FIG. 3 is a cross-sectional view illustrating a configuration of a laminated film used for an exterior body of the present invention.

In FIG. 1, reference numeral 1 denotes a barrier material;
Denotes a base material, 3 denotes an inorganic compound deposited layer, 4 denotes a coating layer, 5 denotes a printing layer, 6 denotes an adhesive layer, and 7 denotes a heat seal layer. Substrate 2
Are sheet-like or film-like materials, such as polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polychlorinated A plastic film or sheet usually used as a packaging material such as vinyl, polyimide, or a copolymer of these polymers can be used. The substrate can be appropriately selected from the above materials depending on the application.

Known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a coloring agent can be added to the substrate 2, and are appropriately added as necessary.

Further, the surface (deposition surface) of the base material 2 may be subjected to surface modification such as corona treatment and anchor coating treatment to improve the adhesion of the deposition layer.

The inorganic compound deposition layer 3 is made of an oxide, nitride, or the like of silicon, aluminum, titanium, zirconium, tin, or the like.
It is made of a simple substance of fluoride or a composite thereof, and is formed by a vacuum deposition method, a sputtering method, a plasma vapor deposition method (CVD).
Method) and the like.

The thickness of the inorganic compound deposited layer 3 depends on the purpose and the second
Depending on the film thickness of the layer (coating layer),
A range of 00 ° is desirable. However, if it is less than 50 °, there is a problem in the continuity of the thin film, and if it exceeds 3000 °, cracks are liable to occur and the flexibility is lowered.

The coating layer 4 is mainly composed of an aqueous solution containing a water-soluble polymer and at least one of (a) at least one metal alkoxide and its hydrolyzate, and (b) tin chloride, or a mixed solution of water / alcohol. And a coating agent. A water-soluble polymer and tin chloride are converted to an aqueous system (water or water /
(Alcohol mixture) A solution obtained by dissolving with a solvent, or a solution obtained by directly treating the metal alkoxide or by preliminarily hydrolyzing the metal alkoxide, is coated on the inorganic compound vapor deposition layer 3 on the plastic substrate 2, and heated. It is dried and formed. Each component contained in the coating agent will be described in detail below.

The water-soluble polymer used for the coating agent in the present invention includes polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (PVA) is used as a coating material for the barrier material of the present invention, the gas barrier properties are most excellent. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and ranges from so-called partially saponified PVA in which acetic acid groups remain to several tens percent to fully saponified PVA in which only a few percent of acetic acid groups remain. And is not particularly limited.

In addition, tin chloride is prepared from stannous chloride (SnC).
l ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and either an anhydride or a hydrate can be used.

Further, the metal alkoxide is represented by a general formula such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], M (OR) _n (M: metal such as Si, Ti, Ai, Zr, R: CH ₃ ,
(An alkyl group such as C ₂ H ₅ ). Among them, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

Each of the above-mentioned components can be added to the coating agent alone or in combination of several components. Further, as long as the barrier property of the coating agent is not impaired, an isocyanate compound, a silane coupling agent, a dispersant, a stabilizer, Known additives such as a viscosity modifier and a colorant can be added.

For example, an isocyanate compound added to a coating agent has two or more isocyanate groups (NCO groups) in its molecule, such as tolylene diisocyanate (TDI), triphenylmethane triisocyanate (TTI), There are monomers such as tetramethylxylene diisocyanate (TMXDI), and polymers and derivatives thereof.

As a method for applying the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, and a spray method are used. The thickness of the film varies depending on the type of the coating agent, but the thickness after drying may be in the range of about 0.01 to 100 μm. When the thickness is 50 μm or more, cracks are easily generated in the film. It is desirable that the thickness be 50 μm.

The barrier material 1 having the above structure is provided in one layer in the laminated film of the present invention. If a higher barrier property is required, the barrier material 1 may be provided in two or more layers. it can.

The printing layer 5 is formed directly on the coating layer 4, and the printing ink for forming the printing layer 5 is not particularly limited, but preferably uses a urethane resin as a binder.

The heat seal layer 7 is made of polyethylene, polypropylene, ethylene copolymer, saturated polyester, etc.
Any resin having heat sealing properties can be used according to the purpose. This heat seal layer 7 may be provided by laminating a material that has been made into a film in advance via an adhesive layer 6 made of a well-known adhesive such as a one- or two-component curable urethane-based adhesive, The resin thus obtained may be laminated by extrusion coating via an adhesive layer 6 made of an anchor agent.

The laminating position of the heat seal layer 7 is on the surface of the coating layer 4 of the barrier material 1 in the illustrated embodiment, but as in the other embodiment shown in FIG. The surface opposite to the coating layer 4) may be used. In the embodiment of FIG. 2, an anchor coat layer 11 is formed on a base material 2, and a sealant layer 7 made of a low-density polyethylene prepared in advance is laminated via a melt-extruded low-density polyethylene 71 as an adhesive layer. , By a so-called sand lamination method.

As described above, the heat seal layer 7
In the case where is formed, as shown in FIG. 2, it is preferable to laminate an exterior material 8 on the surface of the coating layer 4 of the barrier material 1 in order to protect the vapor deposition layer 3 of the barrier material 1. This exterior material 8
Can be used by selecting a film having a stable mechanical strength such as a stretched polyester film, a stretched polypropylene film, a stretched nylon film or the like according to the purpose.

When the exterior material 8 is provided, the printed layer 5 is not formed on the coating layer 4 as shown in FIG.
, And the printing layer 5 is coated with the barrier material 1 as shown in FIG.
May be stacked on the surface of the coating layer 4 and laminated via the adhesive layer 6.

The laminated film obtained as described above is formed as an exterior body having a shape such as a gusset-shaped bag or a pillow packaging bag with the heat sealing layer 7 as an inner surface. Be used with the body.

Example 1 A 12 μm-thick polyethylene terephthalate (PET) was used as a plastic base material, and SiO (silicon monoxide) was used as an evaporation source on the upper surface thereof. Was formed, and a coating liquid having the following composition was further applied by a bar coater, and dried at 120 ° C. for 1 minute with a drier to form a coating layer having a thickness of about 0.5 μm, thereby obtaining a barrier material. .

10. Component of coating liquid Tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ]
89.6 g of hydrochloric acid (0.1N) was added to 4 g, and the mixture was stirred for 30 minutes and hydrolyzed. The hydrolyzed solution (A) having a solid content of 3 wt% (in terms of SiO ₂ ) and 3.0 w of polyvinyl alcohol were added.
A composition in which a t% water / isopropyl alcohol (90/10) solution (B) is mixed.

Next, a urethane-based two-component curable adhesive (A-515, manufactured by Takeda Pharmaceutical Co., Ltd.) was coated on the surface of the coating layer by a gravure method at 4 g / m ^2, and a low density polyethylene film (60 μm) was dry-laminated To produce a laminated film. Using this laminated film, a camera body preliminarily containing a photosensitive material was pillow-wrapped to obtain a camera package.

The oxygen permeability and the water vapor permeability were measured for the laminated film immediately after production and for the laminated film as a package after the camera was packaged. Table 1 shows the results.

Comparative Example 1 A low-density polyethylene film was laminated with an adhesive layer on a vapor-deposited layer under the same configuration and conditions as in Example 1 except that no coating layer was provided to obtain a laminated film. Then, the oxygen permeability and the water vapor permeability were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 2 A polyethylene terephthalate film (12 μm) provided with a printed layer on the back surface was laminated on the coating layer side of the barrier material used in Example 1 by a dry lamination method. A laminated film in which a density polyethylene film (40 μm) was laminated via a molten polyethylene layer (15 μm) was used as an outer package. Then, the same test as in Example 1 was performed. Oxygen permeability,
Table 1 shows the water vapor permeability.

Comparative Example 2 An ethylene-vinyl alcohol copolymer (EVAL) was used instead of the barrier material of Example 2.
Except that EP-F, manufactured by Kuraray Co., Ltd., 15 μm) was used,
A camera package was obtained in the same manner as in Example 2. Then, the same test as in Example 2 was performed. Table 1 shows the oxygen permeability and the water vapor permeability.

[0041]

[Table 1]

[0042]

The camera package of the present invention uses, as the outer package, a laminated film having a barrier material provided with a coating layer on a vapor-deposited surface, instead of a vapor-deposited film provided simply with an inorganic compound vapor-deposited layer. , Even if the thickness of the deposited layer is thin,
A sufficient barrier property can be maintained, and the reduction in the barrier property after packaging is small, making it suitable for packaging a camera body containing a photosensitive material that requires a high barrier property.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a laminated film used in the present invention.

FIG. 2 is a cross-sectional view showing another example of a laminated film used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Barrier material 2 ... Substrate 3 ... Inorganic compound vapor deposition layer 4 ... Coating layer 5 ... Printing layer 6 ... Adhesive layer 7 ... Heat seal layer 8 ... Exterior material

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C23C14 / 20 C23C14 / 20A (56) References JP-A-4-78574 (JP, A) JP-A-5-216175 ( JP, A) JP-A-6-250343 (JP, A) JP-A-5-224358 (JP, A) JP-A-6-43595 (JP, A) JP-A-3-240039 (JP, A) JP JP-A-5-281664 (JP, A) JP-A-3-134655 (JP, A) JP-A 1-267031 (JP, A) JP-A-3-137639 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) G03C 3/00

Claims (4)

(57) [Claims] 1. A camera body in which a photosensitive material is stored in advance,
In a camera package which is hermetically packaged with an exterior body made of a moisture-proof film, the base material has a thickness of 50 to 50 as the exterior body.
Laminate film having a vapor deposited film having an inorganic compound deposition layer of 3000 Å, the barrier material thickness containing a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof is provided with a coating layer of 0.01~50μm the deposition surface A camera package characterized by using: 2. A camera body in which a photosensitive material is stored in advance,
In a camera package which is hermetically packaged with an exterior body made of a moisture-proof film, the base material has a thickness of 50 to 50 as the exterior body.
A vapor-deposited film provided with an inorganic compound vapor-deposited layer having a thickness of 3000 ° has a film thickness of 0.0 including a water-soluble polymer and tin chloride on a vapor-deposited surface.
A camera package comprising a laminated film having a barrier material provided with a coating layer of 1 to 50 μm . 3. The camera packaging according to claim 1, wherein a substrate having an anchor coat layer for vapor deposition of an inorganic compound on a vapor deposition surface is used as a substrate of the barrier material. body. 4. An exterior body on the opposite side of the base material from the deposited layer,
The camera package according to any one of claims 1 to 3, wherein a laminated film provided with an exterior material made of a plastic film is used.