JPH04238024A - Laminated sheet for packing having transparency - Google Patents

Abstract

PURPOSE:To obtain a laminated sheet for packing excellent in transparency, ultraviolet screening properties or ultraviolet absorbability and gas barrier properties. CONSTITUTION:A laminated sheet 8 having ultraviolet screening or absorbing capacity has a thermoplastic resin film 4 having a membrane layer 3 composed of inorg. oxide or a gas barrier layer due to a laminated sheet of said thermoplastic resin film and a gas barrier thermoplastic resin film.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent laminated sheet for packaging used, for example, in extruded tube containers and pouch-type packaging.

0002

[Prior Art] Packaging bodies for enclosing inner fillers that are susceptible to deterioration or deterioration due to the influence of oxygen include, for example,
Packaging laminated sheets are used in which metal foils such as aluminum foils are laminated.

[0003] In addition, packaging bodies for enclosing substances that deteriorate or change in quality due to ultraviolet rays, especially substances containing oils, fats, pigments, etc., are provided with an ultraviolet blocking resin layer or an ultraviolet absorbing resin layer. For example, it is described in Japanese Patent Application Laid-Open No. 63-218049 that the laminated sheet provided therein is utilized.

0004

[Problem to be Solved by the Invention] The laminated sheet in which metal foil such as aluminum foil is laminated has sufficient gas barrier properties, but it is difficult to check the condition of the contents inside the package from the outside. It has the disadvantage of not being possible.

Furthermore, Japanese Patent Laid-Open No. 63-218049 describes an example of a sheet having both gas barrier properties and ultraviolet blocking properties, which has a gas barrier resin layer made of a saponified ethylene-vinyl acetate copolymer and a UV blocking resin layer. A laminated sheet comprising a UV-absorbing resin layer or an ultraviolet-absorbing resin layer has been described, but this laminated sheet does not have sufficient gas barrier performance, and for example, when storing tube containers, etc., the fragrance of the inner filler, etc. It has the disadvantage that the information begins to be lost.

In contrast, the present invention provides transparency that allows the filling inside the package to be seen from the outside, and ultraviolet blocking or ultraviolet absorbing properties that prevent the filling from being deteriorated by ultraviolet rays. The present invention provides a packaging laminated sheet having extremely excellent oxygen barrier properties and extremely excellent storage properties.

[0007]

[Means for Solving the Problems] A transparent laminated sheet for packaging according to the first invention is provided with a gas barrier layer made of a thermoplastic resin film having a thin layer of an inorganic oxide, and has ultraviolet blocking performance. Alternatively, it is made of a laminated sheet with ultraviolet absorption performance.

The transparent laminated sheet for packaging according to the second invention comprises a thermoplastic resin film having a thin inorganic oxide layer and a gas barrier thermoplastic resin laminated on the inorganic oxide thin layer. It is comprised of a laminate sheet that has a gas barrier layer formed by a laminate sheet with a film layer, and has ultraviolet blocking performance or ultraviolet absorption performance.

The transparent laminated sheet for packaging according to the third aspect of the present invention is a thermoplastic resin film having a thin layer of an inorganic oxide, or a thermoplastic resin film having a thin layer of an inorganic oxide and the inorganic oxide. In a packaging laminated sheet comprising a gas barrier layer formed by a laminated sheet with a gas barrier thermoplastic resin film layer laminated to a thin film layer of an object, and having ultraviolet blocking performance or ultraviolet absorption performance. , the thermoplastic resin film having a thin layer of an inorganic oxide is composed of a thermoplastic resin film made of a resin having an -OH group.

[0010] When the transparent laminated sheet for packaging of the present invention having the above structure is used as a pouch-type packaging body, for example, when the laminated sheet is used as a pouch-type packaging body, the surface that becomes the inner circumferential layer of the packaging body is heated. It is made of a resin layer that has sealing properties. For example, when used as a material for forming the body of an extruded tube container, the inner and outer surfaces of the tube are formed of a resin layer that can be heat-sealed to each other.

[0011] Examples of the heat sealant layer in the packaging laminated sheet include low density polyethylene, medium density polyethylene, linear low density polyethylene, ionomer,
carboxyl group-modified polyolefin, polypropylene,
Single layer or composite layer made of transparent general resin such as polyester, nylon, etc. Thickness 60 to 200
A resin layer of about μ size is used, and if desired, one with decorative printing etc. is used.

The thermoplastic resin film having a thin film layer of an inorganic oxide is, for example, a biaxially stretched film of about 9 to 50 μm thick made of polyamide, polyester, polypropylene, etc., and is made of tin oxide, zinc oxide, silicon oxide, Thickness 10 made of indium oxide, titanium oxide, aluminum oxide, etc.
0 to 5000 angstroms, preferably 400 to 10
A film is used in which a thin film layer of about 0.00 angstroms is formed by vacuum deposition, sputtering, chemical vapor deposition, or the like.

In particular, in the third invention, a thin film layer of an inorganic oxide is applied to a thermoplastic resin film made of a resin having an -OH group, such as a polyvinyl alcohol film or an ethylene/vinyl alcohol copolymer resin film. The film that has been formed is utilized. Note that the -OH group-containing thermoplastic resin film that serves as the base material for forming the inorganic oxide thin film layer may be a single-layer resin film or a coating layer of -OH group-containing resin. However, from the viewpoint of suitability for forming a thin layer of inorganic oxide, a single plastic film obtained by extruding a resin containing -OH groups is preferable. suitable. Furthermore, from the point of view of the vapor deposition efficiency of the inorganic oxide thin film layer, that is, the high gas barrier property against the thickness of the inorganic oxide thin film layer, polyvinyl alcohol film is the most suitable, and has good bending resistance. Get results.

[0014] When the inorganic oxide thin film layer is made of silicon oxide, there is very little coloring and high gas barrier properties can be obtained.

[0015] The ultraviolet absorption performance is determined, for example, when organic ultraviolet absorbers such as benzophenone, benzotriazole, salicylate, and acrylate are used in the binder resin 1.
Forming a coating layer with a coating agent added in an amount of about 5 to 10% by weight based on 00 parts by weight, or
This is provided by an adhesive layer made of an adhesive containing the ultraviolet absorber.

[0016] The ultraviolet blocking performance is, for example, titanium oxide,
A solid printing layer using an ink containing 10 to 70 parts by weight of fine powder of inorganic oxides such as iron oxide, zinc oxide, and zirconium oxide mixed with 100 parts by weight of binder resin, or a ready-made printing layer. The inorganic oxide is deposited on a resin film to a thickness of about 1 to 7 microns.

In the transparent laminated sheet for packaging of the present invention, when the gas barrier layer itself made of a thermoplastic resin film having a thin film layer of an inorganic oxide also has UV blocking performance or UV absorbing performance, inorganic oxidation Although it is not necessarily necessary to laminate another resin layer having ultraviolet blocking performance in addition to the gas barrier layer made of a thermoplastic resin film having a thin film layer of Of course, the resin layer having absorption performance may be formed of another resin layer.

[0018] In the second or third invention,
A thermoplastic resin film with gas barrier properties that is laminated on a thermoplastic resin film having a thin layer of inorganic oxide includes:
For example, thermoplastic resin films made of polyvinylidene chloride resin, polyvinylidene chloride copolymer resin, ethylene-vinyl alcohol copolymer resin, polyacrylonitrile resin, polyvinyl alcohol resin, polyamide resin, etc.
Furthermore, it is made of a thermoplastic resin film having a coating layer made of these resins, and preferably has an oxygen permeability of 3.
0cc/m2 ・day ・atm The following are used.

[0019]

EXAMPLES The specific structure of the transparent laminated packaging sheet of the present invention will be explained with reference to manufacturing examples.

Example 1 In FIG. 1, a film was obtained consisting of a biaxially stretched polyester film 1 having a thickness of 12 μm and an ultraviolet blocking resin layer 2 attached to the surface of the biaxially stretched polyester film 1.

The ultraviolet-blocking resin layer 2 is made of a gravure printing ink containing 100 parts by weight of polyester resin (binder resin) and 30 parts by weight of ultrafine particles of a mixture of titanium oxide and iron oxide. Consists of a 2μ thick colorless solid printing layer.

A biaxially stretched polyester film 4 having a thickness of 12 μm and having a vacuum-deposited silicon oxide layer 3 having a thickness of 500 angstroms was also obtained.

Next, the above-mentioned biaxially stretched polyester film 1 having the ultraviolet-blocking resin layer 2 printed on the entire surface and the biaxially stretched polyester film 4 having the vacuum-deposited layer 3 of silicon oxide are coated with ultraviolet rays by solid printing on the entire surface. The barrier resin layer 2 and the vacuum-deposited layer 3 of silicon oxide were bonded to each other by a dry lamination method using a urethane adhesive so as to be in contact with each other, thereby obtaining a composite film designated by reference numeral 5.

Next, an inner layer of polyethylene film 6 with a thickness of 120 μm was applied to one side of the biaxially stretched polyester film in the composite film 5, and an inner layer of polyethylene film 6 with a thickness of 120 μm was applied to the four sides of the biaxially stretched polyester film. The outer layers of the film 7 were adhered to each other by a dry lamination method using a urethane adhesive to obtain a transparent laminated packaging sheet 8, which is an example of the present invention.

Example 2 A film was obtained consisting of a biaxially stretched polyester film having a thickness of 12 μm and an ultraviolet absorbing resin layer attached to the surface of the biaxially stretched polyester film.

The ultraviolet absorbing resin layer is made of a coating agent containing 100 parts by weight of polyvinylidene chloride copolymer resin (resin for binder) and 10 parts by weight of a benzophenone ultraviolet absorber. m
It consists of two coating layers.

A biaxially stretched polyester film having a thickness of 12 μm and having a vacuum-deposited layer of silicon oxide having a thickness of 500 angstroms was also obtained.

Next, the biaxially stretched polyester film having the ultraviolet absorbing resin layer and the biaxially stretched polyester film having the vacuum deposited layer of silicon oxide are separated so that the surfaces of the ultraviolet absorbing resin layer and the vacuum deposited layer of silicon oxide are A composite film was obtained by dry laminating with a urethane adhesive so that they were in contact with each other.

Next, an inner layer made of a polyethylene film having a thickness of 120 μm was added to the biaxially stretched polyester film surface having the ultraviolet absorbing resin layer in the composite film, and a biaxially stretched polyester film having a vacuum-deposited layer of silicon oxide was added. An outer layer made of a polyethylene film having a thickness of 120 μm was adhered to the polyester film surface using a dry lamination method using a urethane adhesive to obtain a transparent packaging laminated sheet, which is an example product of the present invention. .

Comparative Example 1 Ultraviolet blocking properties of gravure printing ink containing ultrafine particles of a mixture of titanium oxide and iron oxide during the manufacturing process of the transparent laminated sheet 8 for extruded tubes of Example 1. A packaging laminated sheet for comparison was obtained by omitting the step of forming the resin layer 2 and having the same configuration as the corresponding portion of the packaging laminated sheet 8 of Example 1 with respect to other configurations.

Manufacture of tube containers After punching the packaging laminated sheets having each transparency obtained in Examples 1 to 2 and Comparative Example 1 to obtain a blank plate for the body of the tube container, the blank was By overlapping the left and right sides of the plates and thermally bonding them, a cylindrical body with a diameter of 35 mm and a height of 150 mm is formed, with the inner layer of the blank plate serving as the inner peripheral surface layer of the tube. did.

Next, the above-mentioned cylindrical body is mounted on a mandrel for forming a tube container, and one end of the cylindrical body is fitted with a truncated conical shoulder and a narrow-necked opening connected thereto, according to a conventional method. The neck and neck are made of low-density polyethylene ``Mirason 16''.
Three types of extruded tube containers having general shapes as shown by reference numeral 9 in FIG. 2 were obtained by injection molding of ``p'' resin.

[Test 1] 50 g of salted squid was sealed in the three types of extruded tube containers obtained, and irradiated with a xenon fade meter for 72 hours. The color difference between the sample and the salted squid before irradiation with a xenon fade meter was measured using a color difference meter. Measurement results [Table 1]
Shown below.

[0034]

[Table 1]

[Test 2] Corn oil with a peroxide value of 0.7 was sealed in the three types of extruded tube containers described above, and after 60 hours of irradiation with a xenon fade meter,
The peroxide value of the corn oil taken out from each tube container was measured. The measurement results are shown in [Table 2].

[0036]

[Table 2]

Example 3 In FIG. 3, a film was obtained consisting of a biaxially stretched polyester film 31 having a thickness of 12 μm and an ultraviolet blocking resin layer 32 attached to the surface of the biaxially stretched polyester film 31.

The ultraviolet blocking resin layer 32 is made of polyvinylidene chloride copolymer resin (binder resin) 100
3g (dry) of a coating agent in which 10 parts by weight of a benzophenone ultraviolet absorber is mixed.
/m2 coating layer.

Further, after forming a vacuum-deposited layer 33 of silicon oxide with a thickness of 500 angstroms on the surface of the biaxially stretched polyester film 34 with a thickness of 12 μm, a vacuum-deposited layer 33 of silicon oxide with a thickness of 20 μm is formed on the surface of the vacuum-deposited silicon oxide layer 33 with a thickness of 20 μm. A composite film 36 was obtained by laminating polyvinylidene chloride resin films 35 using a urethane adhesive.

Furthermore, the 22 sides of the UV-blocking resin layer of the biaxially stretched polyester film 31 and the 35 sides of the polyvinylidene chloride resin film of the composite film 36 are laminated using a urethane adhesive, and then A low density polyethylene resin film 37 with a thickness of 100μ is laminated on the 31 side of the biaxially stretched polyester film using a urethane adhesive, and a low density polyethylene resin film 37 with a thickness of 100μ is laminated on the 34th side of the biaxially stretched polyester film. By laminating the low-density polyethylene resin film 38 using the same urethane adhesive, a transparent laminated packaging sheet 39, which is an example of the present invention, was obtained.

Example 4 In the lamination process of the packaging laminated sheet of Example 3, biaxially oriented polyester having a coating layer (3μ) of polyvinylidene chloride resin was used instead of the 20μ thick polyvinylidene chloride resin film 35. One embodiment of the present invention is carried out by using a film (12μ) and laminating the film using a urethane adhesive so that the surface of the polyvinylidene chloride resin coating layer and the vacuum-deposited layer of silicon oxide are in contact with each other. An example product, a transparent laminated sheet for packaging, was obtained.

Example 5 In the manufacturing process of the packaging laminated sheet of Example 1, instead of the 12 μm thick biaxially stretched polyester film 4 having the 500 angstrom thick silicon oxide vacuum deposited layer 3, a 500 angstrom thick biaxially stretched polyester film 4 was used. The present invention utilizes a biaxially stretched polyvinyl alcohol film with a thickness of 15μ having a vapor-deposited layer of silicon oxide of angstroms, and the other configuration is the same as the corresponding process of the packaging laminated sheet of Example 1. A transparent laminated packaging sheet as an example product was obtained.

Example 6 In the manufacturing process of a packaging laminated sheet with the laminated structure of Example 3, instead of the biaxially stretched polyester film 34 having a thickness of 12μ and having a vacuum-deposited layer 33 of silicon oxide having a thickness of 500 angstroms, Utilizing a 12μ thick biaxially stretched ethylene-vinyl alcohol copolymer resin film having a 600 angstrom thick silicon oxide vapor deposited layer,
A transparent laminate sheet for packaging, which is an example product of the present invention, was obtained which had all other structures the same as the corresponding parts of the extruded laminate material for tubes of Example 3.

[0044]

Effects of the Invention The transparent laminated sheet for packaging of the present invention comprises a thermoplastic resin film having a thin layer of inorganic oxide, and has ultraviolet blocking performance or ultraviolet absorbing performance. , which has both excellent gas barrier properties and ultraviolet blocking or absorption properties, and in particular, the inner filler containing oils, fats, pigments, etc. will not deteriorate due to ultraviolet rays, and it has good storage properties. A package having the following properties is obtained.

The transparent laminated sheet for packaging according to the second invention comprises a thermoplastic resin film having a thin inorganic oxide layer and a gas barrier thermoplastic resin laminated on the inorganic oxide thin layer. It is equipped with a gas barrier layer made of a laminated sheet with a film layer, and has ultraviolet blocking performance or ultraviolet absorption performance, the gas barrier property being a thin film layer of an inorganic oxide and the thermoplastic resin film layer having gas barrier properties. For example, it may be heat-sealed in a folded state, or
Even if pinholes or cracks occur in the thin layer of inorganic oxide when the package is repeatedly bent, the gas barrier properties laminated on the thin layer of inorganic oxide will Due to the compensating action of the thermoplastic resin film layer, the gas barrier properties of the gas barrier layer function normally, resulting in a package that exhibits extremely excellent storage properties.

The transparent laminated sheet for packaging according to the third invention is such that the thermoplastic resin film having a thin layer of an inorganic oxide is made of a thermoplastic resin film made of a resin having an -OH group, and the thermoplastic resin film has a thin film layer of an inorganic oxide. At the vapor deposition interface of the oxide, a bonding state is created between the resin and the -OH group, thereby providing excellent adhesion strength between the film and the metal oxide.

[0047]

Effects of the Invention The transparent laminated sheet for packaging of the present invention has such transparency that the encapsulation of the contents of the package by the laminated sheet can be visually observed from the outside, and is also resistant to ultraviolet rays and oxygen. Even if the filling material is susceptible to deterioration due to the influence of water, the packaging material can be stored without deterioration, resulting in a packaging product with high utility value.

[Brief explanation of the drawing]

FIG. 1: One of the transparent laminated packaging sheets of the present invention
FIG. 3 is a cross-sectional view schematically showing a laminated structure of an example product.

FIG. 2 is a front view showing the general shape of an extruded tube container in which the transparent laminated packaging sheet of the present invention is used for the container body.

FIG. 3: One of the transparent laminated packaging sheets of the present invention
FIG. 3 is a cross-sectional view schematically showing a laminated structure of an example product.

[Explanation of symbols]

1 Biaxially oriented polyester film 2 Ultraviolet blocking resin layer 3 Vacuum deposited silicon oxide layer 4 Biaxially oriented polyester film 5 Composite film 6 Inner layer 7 Outer layer 8 Transparent laminated sheet for packaging 9 Extruded tube container

Claims (3)

[Claims] 1. A transparent laminated sheet for packaging, comprising a gas barrier layer made of a thermoplastic resin film having a thin layer of an inorganic oxide, and having ultraviolet blocking or absorbing properties. 2. A gas barrier layer comprising a laminated sheet of a thermoplastic resin film having a thin inorganic oxide layer and a thermoplastic resin film layer having gas barrier properties laminated on the inorganic oxide thin layer. 1. A transparent laminated sheet for packaging, characterized in that it has ultraviolet blocking performance or ultraviolet absorbing performance. 3. The transparent laminated sheet for packaging according to claim 1 or 2, wherein the thermoplastic resin film having the thin inorganic oxide layer is a thermoplastic resin film made of a resin having an -OH group.